WorldWideScience

Sample records for meridional enthalpy transports

  1. Meridional Flow Observations: Implications for the current Flux Transport Models

    International Nuclear Information System (INIS)

    Gonzalez Hernandez, Irene; Komm, Rudolf; Kholikov, Shukur; Howe, Rachel; Hill, Frank

    2011-01-01

    Meridional circulation has become a key element in the solar dynamo flux transport models. Available helioseismic observations from several instruments, Taiwan Oscillation Network (TON), Global Oscillation Network Group (GONG) and Michelson Doppler Imager (MDI), have made possible a continuous monitoring of the solar meridional flow in the subphotospheric layers for the last solar cycle, including the recent extended minimum. Here we review some of the meridional circulation observations using local helioseismology techniques and relate them to magnetic flux transport models.

  2. Radial Transport and Meridional Circulation in Accretion Disks

    Energy Technology Data Exchange (ETDEWEB)

    Philippov, Alexander A. [Department of Astrophysical Sciences, Princeton University, Ivy Lane, Princeton, NJ 08540 (United States); Rafikov, Roman R., E-mail: sashaph@princeton.edu [Institute for Advanced Study, Einstein Drive, Princeton, NJ 08540 (United States)

    2017-03-10

    Radial transport of particles, elements and fluid driven by internal stresses in three-dimensional (3D) astrophysical accretion disks is an important phenomenon, potentially relevant for the outward dust transport in protoplanetary disks, origin of the refractory particles in comets, isotopic equilibration in the Earth–Moon system, etc. To gain better insight into these processes, we explore the dependence of meridional circulation in 3D disks with shear viscosity on their thermal stratification, and demonstrate a strong effect of the latter on the radial flow. Previous locally isothermal studies have normally found a pattern of the radial outflow near the midplane, switching to inflow higher up. Here we show, both analytically and numerically, that a flow that is inward at all altitudes is possible in disks with entropy and temperature steeply increasing with height. Such thermodynamic conditions may be typical in the optically thin, viscously heated accretion disks. Disks in which these conditions do not hold should feature radial outflow near the midplane, as long as their internal stress is provided by the shear viscosity. Our results can also be used for designing hydrodynamical disk simulations with a prescribed pattern of the meridional circulation.

  3. Interpreting the implied meridional oceanic energy transport in AMIP

    International Nuclear Information System (INIS)

    Randall, D.A.; Gleckler, P.J.

    1993-09-01

    The Atmospheric Model Intercomparison Project (AMIP) was outlined in Paper No. CLIM VAR 2.3 (entitled open-quote The validation of ocean surface heat fluxes in AMIP') of these proceedings. Preliminary results of AMIP subproject No. 5 were also summarized. In particular, zonally averaged ocean surface heat fluxes resulting from various AMIP simulations were intercompared, and to the extent possible they were validated with uncertainties in observationally-based estimates of surface heat fluxes. The intercomparison is continued in this paper by examining the Oceanic Meridional Energy Transport (OMET) implied by the net surface heat fluxes of the AMIP simulations. As with the surface heat fluxes of the AMIP simulations. As with the surface heat fluxes, the perspective here will be very cursory. The annual mean implied ocean heat transport can be estimated by integrating the zonally averaged net ocean surface heat flux, N sfc , from one pole to the other. In AGCM simulations (and perhaps reality), the global mean N sfc is typically not in exact balance when averaged over one or more years. Because of this, an important assumption must be made about changes in the distribution of energy in the oceans. Otherwise, the integration will yield a non-zero transport at the endpoint of integration (pole) which is not physically realistic. Here the authors will only look at 10-year means of the AMIP runs, and for simplicity they assume that any long term imbalance in the global averaged N sfc will be sequestered (or released) over the global ocean. Tests have demonstrated that the treatment of how the global average energy imbalance is assumed to be distributed is important, especially when the long term imbalances are in excess of 10 W m -2 . However, this has not had a substantial impact on the qualitative features of the implied heat transport of the AMIP simulations examined thus far

  4. South Atlantic meridional transports from NEMO-based simulations and reanalyses

    Science.gov (United States)

    Mignac, Davi; Ferreira, David; Haines, Keith

    2018-02-01

    The meridional heat transport (MHT) of the South Atlantic plays a key role in the global heat budget: it is the only equatorward basin-scale ocean heat transport and it sets the northward direction of the global cross-equatorial transport. Its strength and variability, however, are not well known. The South Atlantic transports are evaluated for four state-of-the-art global ocean reanalyses (ORAs) and two free-running models (FRMs) in the period 1997-2010. All products employ the Nucleus for European Modelling of the Oceans (NEMO) model, and the ORAs share very similar configurations. Very few previous works have looked at ocean circulation patterns in reanalysis products, but here we show that the ORA basin interior transports are consistently improved by the assimilated in situ and satellite observations relative to the FRMs, especially in the Argo period. The ORAs also exhibit systematically higher meridional transports than the FRMs, which is in closer agreement with observational estimates at 35 and 11° S. However, the data assimilation impact on the meridional transports still greatly varies among the ORAs, leading to differences up to ˜ 8 Sv and 0.4 PW in the South Atlantic Meridional Overturning Circulation and the MHTs, respectively. We narrow this down to large inter-product discrepancies in the western boundary currents (WBCs) at both upper and deep levels explaining up to ˜ 85 % of the inter-product differences in MHT. We show that meridional velocity differences, rather than temperature differences, in the WBCs drive ˜ 83 % of this MHT spread. These findings show that the present ocean observation network and data assimilation schemes can be used to consistently constrain the South Atlantic interior circulation but not the overturning component, which is dominated by the narrow western boundary currents. This will likely limit the effectiveness of ORA products for climate or decadal prediction studies.

  5. The influence of meridional ice transport on Europa's ocean stratification and heat content

    Science.gov (United States)

    Zhu, P.; Manucharyan, G.; Thompson, A. F.; Goodman, J. C.; Vance, S.

    2017-12-01

    Jupiter's moon Europa likely hosts a saltwater ocean beneath its icy surface. Geothermal heating and rotating convection in the ocean may drive a global overturning circulation that redistributes heat vertically and meridionally, preferentially warming the ice shell at the equator. Here we assess thepreviously unconstrained influence of ocean-ice coupling on Europa's ocean stratification and heat transport. We demonstrate that a relatively fresh layer can form at the ice-ocean interface due to a meridional ice transport forced by the differential ice shell heating between the equator and the poles. We provide analytical and numerical solutions for the layer's characteristics, highlighting their sensitivity to critical ocean parameters. For a weakly turbulent and highly saline ocean, a strong buoyancy gradient at the base of the freshwater layer can suppress vertical tracer exchange with the deeper ocean. As a result, the freshwater layer permits relatively warm deep ocean temperatures.

  6. A modelling study of the Bjerknes compensation in the meridional heat transport in a freshening ocean

    Directory of Open Access Journals (Sweden)

    Haijun Yang

    2013-05-01

    Full Text Available The compensation between the meridional heat transports in the atmosphere and ocean is studied through a coupled model's water-hosing experiments. It is found that the atmospheric heat transport (AHT change compensates the oceanic heat transport (OHT change very well in the extratropics, while the former over-compensates the latter in the tropics. Similar to previous studies, the fresh water input in the high latitude Atlantic weakens the Atlantic meridional overturning circulation and thus the northward Atlantic OHT significantly, leading to a warming (cooling in sea surface temperature in the Southern (Northern Hemisphere and in turn a southward shift of atmospheric convection. This results in an enhanced Hadley Cell (HC and stronger northward AHT, compensating the reduced Atlantic OHT. Meanwhile, the wind-driven Subtropical Cell in the Indo-Pacific oceans is enhanced in response to the HC change, increasing the northward OHT in the Indo-Pacific, which partly offsets the reduced OHT in the Atlantic. The response in the Indo-Pacific is responsible for the overcompensation of the AHT to the global OHT. The Held's mechanism works very well in the tropical Indo-Pacific in our experiments. This is substantially different from previous studies.

  7. Effects of Solar Geoengineering on Meridional Energy Transport and the ITCZ

    Science.gov (United States)

    Russotto, R. D.; Ackerman, T. P.; Frierson, D. M.

    2016-12-01

    The polar amplification of warming and the ability of the intertropical convergence zone (ITCZ) to shift to the north or south are two very important problems in climate science. Examining these behaviors in global climate models (GCMs) running solar geoengineering experiments is helpful not only for predicting the effects of solar geoengineering, but also for understanding how these processes work under increased CO2. Both polar amplification and ITCZ shifts are closely related to the meridional transport of moist static energy (MSE) by the atmosphere. In this study we examine changes in MSE transport in 10 fully coupled GCMs in Experiment G1 of the Geoengineering Model Intercomparison Project, in which the solar constant is reduced to compensate for abruptly quadrupled CO2 concentrations. In this experiment, poleward MSE transport decreases relative to preindustrial conditions in all models, in contrast to the CMIP5 abrupt4xCO2 experiment, in which poleward MSE transport increases. The increase in poleward MSE transport under increased CO2 is due to latent heat transport, as specific humidity increases faster in the tropics than at the poles; this mechanism is not present under G1 conditions, so the reduction in dry static energy transport due to a weakened equator-to-pole temperature gradient leads to weaker energy transport overall. Changes in cross-equatorial MSE transport in G1, meanwhile, are anticorrelated with shifts in the ITCZ. The northward ITCZ shift in G1 is 0.14 degrees in the multi-model mean and ranges from -0.33 to 0.89 degrees between the models. We examine the specific forcing and feedback terms responsible for changes in MSE transport in G1 by running experiments with a moist energy balance model. This work will help identify the largest sources of uncertainty regarding ITCZ shifts under solar geoengineering, and will help improve our understanding of the reasons for the residual polar amplification that occurs in the G1 experiment.

  8. Mechanisms of meridional transport processes in the tropical Atlantic; Mechanismen meridionaler Transportprozesse im tropischen Atlantik

    Energy Technology Data Exchange (ETDEWEB)

    Kroeger, J.

    2001-07-01

    Meridional transport processes of water masses and tracers in the subtropical and tropical Atlantic are investigated using a regional eddy resolving model of the wind driven and thermohaline circulation. Analytical emphasis is on float simulations in the model which, complementary to Eulerian means, represent the Lagrangian view and give further insight into the spreading and pathways of characteristic water masses in this area. In the tropics and subtropics shallow 3-dimensional circulation cells are superimposed on the northward warm water transfer within the deep reaching thermohaline overturning cell (MOC) as part of the global ''Conveyor Belt''. Under present-day climate conditions the model shows that the equatorial thermocline is exclusively ventilated by subsurface flow within the tropical-subtropical cell (STC) of the South Atlantic. Only with a prescribed ''Conveyor-off''-Mode the STC of the North Atlantic contributes to this ventilation process with equal amounts. Throughout the year the interhemispheric transport of surface and central water masses of South Atlantic origin into the Caribbean Sea is dominated by zonal detours to the east as a consequence of the interplay of several retroflection events occuring in the North Atlantic. The eulerian mean flow field in the deep layer postulates the interhemispheric mass transport into the South Atlantic to be confined entirely to the western boundary, whereas Lagrangian means indicate intermittent eastward excursions along the equator, related to seasonally alternating zonal currents due to long Rossby waves. It was suggested that the observed characteristic eastward maximum of tracer concentrations along the equator is a consequence of rectifying effects of single or interacting equatorial waves. The model does not validate this hypothesis. The response to transport anomalies of subpolar origin and long periodicity is subject to different time-scales in both

  9. Heat transport modeling for the design of a low enthalpy open-loop system

    Directory of Open Access Journals (Sweden)

    Leonardo Piccinini

    2012-12-01

    Full Text Available A case study of hydrogeological characterization and heat transport modeling for the design of a low enthalpy system in the Province of Treviso (Italy is here presented. It is an open loop system that pumps and re-injects groundwater from a confined aquifer of the high Veneto plain. This type of systems is the most efficient in terms of yield, but its construction is highly conditioned by the availability of groundwater resource and by the environmental laws related to groundwater exploitation. Groundwater flow modeling with MODFLOW 2005 led to a good aquifer parameters estimation, by means of the quantitative calibration of a pumping test made on the pumping well and an observation piezometer. Then, with the heat transport modeling with SEAWAT 4 the distance between pumping well and re-injecting well has been optimized, avoiding so the thermal feedback effect. The lack of sitespecific data for dispersivity parameters has been solved through a sensitivity analysis on the main dispersivity parameters of heat transport. Finally, in order to comply with the environmental laws, a long-term forecasting simulation (duration of 20 years has been set up in order to evaluate the open loop system thermal impact on the aquifer. The obtained results put in evidence that the design of low enthalpy systems strongly needs a detailed hydrogeological characterization of the aquifer interested by the pumping and that numerical modeling is the most effective tool in support of the definition of the optimal distance between pumping and re-injecting wells in the open loop systems.

  10. The effect on Arctic climate of atmospheric meridional energy-transport changes studied based on the CESM climate model

    Science.gov (United States)

    Grand Graversen, Rune

    2017-04-01

    The Arctic amplification of global warming, and the pronounced Arctic sea-ice retreat constitute some of the most alarming signs of global climate change. These Arctic changes are likely a consequence of a combination of several processes, for instance enhanced uptake of solar radiation in the Arctic due to a decrease of sea ice (the ice-albedo feedback), and increase in the local Arctic greenhouse effect due to enhanced moister flux from lower latitudes. Many of the proposed processes appear to be dependent on each other, for instance an increase in water-vapour advection to the Arctic enhances the greenhouse effect in the Arctic and the longwave radiation to the surface, leading to sea-ice melt and enhancement of the ice-albedo feedback. The effects of albedo changes and other radiative feedbacks have been investigated in earlier studies based on model experiments designed to examine these effects specifically. Here we instead focus on the effects of meridional transport changes into the Arctic, both of moister and dry-static energy. Hence we here present results of model experiments with the CESM climate model designed specifically to extract the effects of the changes of the two transport components. In the CESM model the moister transport to the Arctic increases, whereas the dry-static transport decreases in response to a doubling of CO2. This is in agreement with other model results. The model is now forced with these transport changes of water-vapour and dry-static energy associated with a CO2 doubling. The results show that changes of the water-vapour transport lead to Arctic warming. This is partly a consequence of the ice-albedo feedback due to sea-ice melt caused by the change of the water-vapour advection. The changes of the dry-static transport lead to Arctic cooling, which however is smaller than the warming induced by the water-vapour component. Hence this study support the hypothesis that changes in the atmospheric circulation contribute to the

  11. Interannual to Decadal Variability of Meridional Transports Across the SAMOC Basin Wide Array (SAMBA) in Simulations with an Eddy-resolving Global Ocean Model

    Science.gov (United States)

    Campos, E. J.; Ambrizzi, T.

    2016-02-01

    Results of numerical experiments with ocean general circulation models show increasing trends in the Agulhas leakage and in the meridional heat transport in the South Atlantic. To further investigate impacts of interannual to interdecadal changes in the wind forcing on the circulation and meridional transports in the South Atlantic, a set of simulations is conducted with an eddy-resolving global implementation of the Hybrid Coordinate Ocean Model (HYCOM). Firstly, a climatological experiment is run, forced with monthly means of the NCEP Reanalysis products, with no interannual variability. The last ten years of a two-decades run are then analyzed. The mean circulation patterns in the South Atlantic are well represented, as compared with observations and results of other models. The outputs show no long term trends, ruling out the hypothesis of any noticeable model's internal drift. Another experiments is then run, forced with interannual variability, from 1949 to the present. The results are compared with those of the climatological experiment, focusing on the circulation, the inter-ocean exchanges, the Agulhas leakage and the meridional transports in the South Atlantic.

  12. The Coupled Mars Dust and Water Cycles: Understanding How Clouds Affect the Vertical Distribution and Meridional Transport of Dust and Water.

    Science.gov (United States)

    Kahre, M. A.

    2015-01-01

    The dust and water cycles are crucial to the current Martian climate, and they are coupled through cloud formation. Dust strongly impacts the thermal structure of the atmosphere and thus greatly affects atmospheric circulation, while clouds provide radiative forcing and control the hemispheric exchange of water through the modification of the vertical distributions of water and dust. Recent improvements in the quality and sophistication of both observations and climate models allow for a more comprehensive understanding of how the interaction between the dust and water cycles (through cloud formation) affects the dust and water cycles individually. We focus here on the effects of clouds on the vertical distribution of dust and water, and how those vertical distributions control the net meridional transport of water. For this study, we utilize observations of temperature, dust and water ice from the Mars Climate Sounder (MCS) on the Mars Reconnaissance Orbiter (MRO) combined with the NASA ARC Mars Global Climate Model (MGCM). We demonstrate that the magnitude and nature of the net meridional transport of water between the northern and southern hemispheres during NH summer is sensitive to the vertical structure of the simulated aphelion cloud belt. We further examine how clouds influence the atmospheric thermal structure and thus the vertical structure of the cloud belt. Our goal is to identify and understand the importance of radiative/dynamic feedbacks due to the physical processes involved with cloud formation and evolution on the current climate of Mars.

  13. Meridional transport of magnetic flux in the solar wind between 1 and 10 AU: a theoretical analysis

    International Nuclear Information System (INIS)

    Pizzo, V.J.; Goldstein, B.E.

    1987-01-01

    Pioneer 10 observations suggest that the mean (longitudinally averaged) solar wind azimuthal field strength, B/sub phi/, near the ecliptic plane falls off more rapidly with heliocentric distance than would be expected in a classic Parker expansion, showing a deficit of 10--20% (as compared to the projected 1-AU value) by 10 AU. Though this observational interpretation has been challenged by subsequent analyses of Voyager data, it has nevertheless stimulated efforts to explain the inferred deficit on the basis of systematic north-south magnetic pressure gradients generated by the differential spiral wrapping of magnetic field lines in interplanetary space. We reexamine this issue from the theoretical perspective using a three-dimensional MHD nonlinear numerical model for steady, corotating flow. For realistic solar wind parameters we find that a purely axisymmetric expansion is capable of producing sizable magnetic flux deficits only when there are substantial meridional gradients in mean flow conditions localized about the ecliptic plane near the sun. Even then the match between plausible flow states and significant mean B/sub phi/ deficit is achieved over such a limited parameter range that it is unlikely this mechanism alone can produce deficits of the magnitude inferred from the Pioneer data

  14. Cloud Effects on Meridional Atmospheric Energy Budget Estimated from Clouds and the Earth's Radiant Energy System (CERES) Data

    Science.gov (United States)

    Kato, Seiji; Rose, Fred G.; Rutan, David A.; Charlock, Thomas P.

    2008-01-01

    The zonal mean atmospheric cloud radiative effect, defined as the difference of the top-of-atmosphere (TOA) and surface cloud radiative effects, is estimated from three years of Clouds and the Earth's Radiant Energy System (CERES) data. The zonal mean shortwave effect is small, though it tends to be positive (warming). This indicates that clouds increase shortwave absorption in the atmosphere, especially in midlatitudes. The zonal mean atmospheric cloud radiative effect is, however, dominated by the longwave effect. The zonal mean longwave effect is positive in the tropics and decreases with latitude to negative values (cooling) in polar regions. The meridional gradient of cloud effect between midlatitude and polar regions exists even when uncertainties in the cloud effect on the surface enthalpy flux and in the modeled irradiances are taken into account. This indicates that clouds increase the rate of generation of mean zonal available potential energy. Because the atmospheric cooling effect in polar regions is predominately caused by low level clouds, which tend to be stationary, we postulate that the meridional and vertical gradients of cloud effect increase the rate of meridional energy transport by dynamics in the atmosphere from midlatitude to polar region, especially in fall and winter. Clouds then warm the surface in polar regions except in the Arctic in summer. Clouds, therefore, contribute in increasing the rate of meridional energy transport from midlatitude to polar regions through the atmosphere.

  15. The Mars Dust and Water Cycles: Investigating the Influence of Clouds on the Vertical Distribution and Meridional Transport of Dust and Water.

    Science.gov (United States)

    Kahre, M. A.; Haberle, R. M.; Hollingsworth, J. L.; Brecht, A. S.; Urata, R.

    2015-01-01

    The dust and water cycles are critical to the current Martian climate, and they interact with each other through cloud formation. Dust modulates the thermal structure of the atmosphere and thus greatly influences atmospheric circulation. Clouds provide radiative forcing and control the net hemispheric transport of water through the alteration of the vertical distributions of water and dust. Recent advancements in the quality and sophistication of both climate models and observations enable an increased understanding of how the coupling between the dust and water cycles (through cloud formation) impacts the dust and water cycles. We focus here on the effects of clouds on the vertical distributions of dust and water and how those vertical distributions control the net meridional transport of water. We utilize observations of temperature, dust and water ice from the Mars Climate Sounder (MCS) on the Mars Reconnaissance Orbiter (MRO) and the NASA ARC Mars Global Climate Model (MGCM) to show that the magnitude and nature of the hemispheric exchange of water during NH summer is sensitive to the vertical structure of the simulated aphelion cloud belt. Further, we investigate how clouds influence atmospheric temperatures and thus the vertical structure of the cloud belt. Our goal is to isolate and understand the importance of radiative/dynamic feedbacks due to the physical processes involved with cloud formation and evolution on the current climate of Mars.

  16. On the Currents and Transports Connected with the Atlantic Meridional Overtuning Circulation in the Subpolar North Atlantic

    Science.gov (United States)

    2013-08-14

    conveyor belt , Science, 328, 1507–1511. Lumpkin, R., K. G. Speer, and K. P. Koltermann (2008), Transport across 48N in the Atlantic Ocean, J. Phys...Fleet Numerical Meteorology and Oceanography Center 3 hourly, 0.5 Navy Operational Global Atmo- spheric Prediction System (NOGAPS [Rosmond et al...Smith (2007), Resolution convergence and sensitivity studies with North Atlantic circulation models. Part I: The western boundary current system

  17. The Observed Relationship Between Water Vapor and Ozone in the Tropical Tropopause Saturation Layer and the Influence of Meridional Transport

    Science.gov (United States)

    Selkirk, Henry B.; Schoeberl, M. R.; Olsen, M. A.; Douglass, A. R.

    2011-01-01

    We examine balloonsonde observations of water vapor and ozone from three Ticosonde campaigns over San Jose, Costa Rica [10 N, 84 W] during northern summer and a fourth during northern winter. The data from the summer campaigns show that the uppermost portion of the tropical tropopause layer between 360 and 380 K, which we term the tropopause saturation layer or TSL, is characterized by water vapor mixing ratios from proximately 3 to 15 ppmv and ozone from approximately 50 ppbv to 250 ppbv. In contrast, the atmospheric water vapor tape recorder at 380 K and above displays a more restricted 4-7 ppmv range in water vapor mixing ratio. From this perspective, most of the parcels in the TSL fall into two classes - those that need only additional radiative heating to rise into the tape recorder and those requiring some combination of additional dehydration and mixing with drier air. A substantial fraction of the latter class have ozone mixing ratios greater than 150 ppbv, and with water vapor greater than 7 ppmv this air may well have been transported into the tropics from the middle latitudes in conjunction with high-amplitude equatorial waves. We examine this possibility with both trajectory analysis and transport diagnostics based on HIRDLS ozone data. We apply the same approach to study the winter season. Here a very different regime obtains as the ozone-water vapor scatter diagram of the sonde data shows the stratosphere and troposphere to be clearly demarcated with little evidence of mixing in of middle latitude air parcels.

  18. Impact of the new equation of state of seawater (TEOS-10) on the estimates of water mass mixture and meridional transport in the Atlantic Ocean

    Science.gov (United States)

    Almeida, Lucas; de Azevedo, José Luiz Lima; Kerr, Rodrigo; Araujo, Moacyr; Mata, Mauricio M.

    2018-03-01

    The equation of state of seawater (EOS) provides a simple way to link the properties of seawater that are the most important for ocean dynamics and the ocean-atmosphere climate system. In 2010, the set of equations used to derive all thermodynamic properties of seawater were updated using a thermodynamic approach. The new approach, named TEOS-10, results in better estimates of seawater properties, such as salinity and temperature, when compared to the previous EOS version (EOS-80). Since several physical processes in the oceans are driven by these properties, improvements in the EOS performance are expected to lead to a better and more realistic representation of the ocean. This work focuses on assessing the main differences of the: (i) contribution of water masses to a total mixture, (ii) baroclinic velocity, and (iii) volume and heat transport, as calculated by the EOS-80 and by the TEOS-10, along four zonal transects at 26.5°N, 10°N, 11°S, and 34.5°S in the Atlantic Ocean. The density differences (always between TEOS-10 and EOS-80) increase with depth and hence the results indicate that the most significant difference in the water mass contributions was found for Antarctic Bottom Water. Within that layer, the differences reach up to 10% on its fraction of the mixture when calculated by the TEOS-10, although the difference in the North Atlantic Deep Water contribution was not negligible either. The estimated baroclinic velocities showed considerable differences in all studied areas, being more significant over boundary current systems. The Gulf Stream presented lower velocity, while the Brazil Current presented increasing velocity when using TEOS-10. The comparison between values computed for volume transported by the Atlantic Meridional Overturning Circulation showed a total difference of about +6%, which cannot be neglected when considering the space and time variability involved. The heat transport showed significant differences in the study areas at the

  19. Probing stratospheric transport and chemistry with new balloon and aircraft observations of the meridional and vertical N2O isotope distribution

    Directory of Open Access Journals (Sweden)

    J. Kaiser

    2006-01-01

    Full Text Available A comprehensive set of stratospheric balloon and aircraft samples was analyzed for the position-dependent isotopic composition of nitrous oxide (N2O. Results for a total of 220 samples from between 1987 and 2003 are presented, nearly tripling the number of mass-spectrometric N2O isotope measurements in the stratosphere published to date. Cryogenic balloon samples were obtained at polar (Kiruna/Sweden, 68° N, mid-latitude (southern France, 44° N and tropical sites (Hyderabad/India, 18° N. Aircraft samples were collected with a newly-developed whole air sampler on board of the high-altitude aircraft M55 Geophysica during the EUPLEX 2003 campaign. For mixing ratios above 200 nmol mol−1, relative isotope enrichments (δ values and mixing ratios display a compact relationship, which is nearly independent of latitude and season and which can be explained equally well by Rayleigh fractionation or mixing. However, for mixing ratios below 200 nmol mol−1 this compact relationship gives way to meridional, seasonal and interannual variations. A comparison to a previously published mid-latitude balloon profile even shows large zonal variations, justifying the use of three-dimensional (3-D models for further data interpretation. In general, the magnitude of the apparent fractionation constants (i.e., apparent isotope effects increases continuously with altitude and decreases from the equator to the North Pole. Only the latter observation can be understood qualitatively by the interplay between the time-scales of N2O photochemistry and transport in a Rayleigh fractionation framework. Deviations from Rayleigh fractionation behavior also occur where polar vortex air mixes with nearly N2O-free upper stratospheric/mesospheric air (e.g., during the boreal winters of 2003 and possibly 1992. Aircraft observations in the polar vortex at mixing ratios below 200 nmol mol−1 deviate from isotope variations expected for both Rayleigh fractionation and two

  20. High enthalpy gas dynamics

    CERN Document Server

    Rathakrishnan, Ethirajan

    2014-01-01

    This is an introductory level textbook which explains the elements of high temperature and high-speed gas dynamics. written in a clear and easy to follow style, the author covers all the latest developments in the field including basic thermodynamic principles, compressible flow regimes and waves propagation in one volume covers theoretical modeling of High Enthalpy Flows, with particular focus on problems in internal and external gas-dynamic flows, of interest in the fields of rockets propulsion and hypersonic aerodynamics High enthalpy gas dynamics is a compulsory course for aerospace engine

  1. Atlantic Meridional Overturning Circulation slowdown cooled the subtropical ocean.

    Science.gov (United States)

    Cunningham, Stuart A; Roberts, Christopher D; Frajka-Williams, Eleanor; Johns, William E; Hobbs, Will; Palmer, Matthew D; Rayner, Darren; Smeed, David A; McCarthy, Gerard

    2013-12-16

    [1] Observations show that the upper 2 km of the subtropical North Atlantic Ocean cooled throughout 2010 and remained cold until at least December 2011. We show that these cold anomalies are partly driven by anomalous air-sea exchange during the cold winters of 2009/2010 and 2010/2011 and, more surprisingly, by extreme interannual variability in the ocean's northward heat transport at 26.5°N. This cooling driven by the ocean's meridional heat transport affects deeper layers isolated from the atmosphere on annual timescales and water that is entrained into the winter mixed layer thus lowering winter sea surface temperatures. Here we connect, for the first time, variability in the northward heat transport carried by the Atlantic Meridional Overturning Circulation to widespread sustained cooling of the subtropical North Atlantic, challenging the prevailing view that the ocean plays a passive role in the coupled ocean-atmosphere system on monthly-to-seasonal timescales.

  2. GASP: A computer code for calculating the thermodynamic and transport properties for ten fluids: Parahydrogen, helium, neon, methane, nitrogen, carbon monoxide, oxygen, fluorine, argon, and carbon dioxide. [enthalpy, entropy, thermal conductivity, and specific heat

    Science.gov (United States)

    Hendricks, R. C.; Baron, A. K.; Peller, I. C.

    1975-01-01

    A FORTRAN IV subprogram called GASP is discussed which calculates the thermodynamic and transport properties for 10 pure fluids: parahydrogen, helium, neon, methane, nitrogen, carbon monoxide, oxygen, fluorine, argon, and carbon dioxide. The pressure range is generally from 0.1 to 400 atmospheres (to 100 atm for helium and to 1000 atm for hydrogen). The temperature ranges are from the triple point to 300 K for neon; to 500 K for carbon monoxide, oxygen, and fluorine; to 600 K for methane and nitrogen; to 1000 K for argon and carbon dioxide; to 2000 K for hydrogen; and from 6 to 500 K for helium. GASP accepts any two of pressure, temperature and density as input conditions along with pressure, and either entropy or enthalpy. The properties available in any combination as output include temperature, density, pressure, entropy, enthalpy, specific heats, sonic velocity, viscosity, thermal conductivity, and surface tension. The subprogram design is modular so that the user can choose only those subroutines necessary to the calculations.

  3. High enthalpy hypersonic boundary layer flow

    Science.gov (United States)

    Yanow, G.

    1972-01-01

    A theoretical and experimental study of an ionizing laminar boundary layer formed by a very high enthalpy flow (in excess of 12 eV per atom or 7000 cal/gm) with allowance for the presence of helium driver gas is described. The theoretical investigation has shown that the use of variable transport properties and their respective derivatives is very important in the solution of equilibrium boundary layer equations of high enthalpy flow. The effect of low level helium contamination on the surface heat transfer rate is minimal. The variation of ionization is much smaller in a chemically frozen boundary layer solution than in an equilibrium boundary layer calculation and consequently, the variation of the transport properties in the case of the former was not essential in the integration. The experiments have been conducted in a free piston shock tunnel, and a detailed study of its nozzle operation, including the effects of low levels of helium driver gas contamination has been made. Neither the extreme solutions of an equilibrium nor of a frozen boundary layer will adequately predict surface heat transfer rate in very high enthalpy flows.

  4. Effects of the Observed Meridional Flow Variations since 1996 on the Sun's Polar Fields

    Science.gov (United States)

    Hathaway, David H.; Upton, Lisa

    2013-01-01

    The cause of the low and extended minimum in solar activity between Sunspot Cycles 23 and 24 was the small size of Sunspot Cycle 24 itself - small cycles start late and leave behind low minima. Cycle 24 is small because the polar fields produced during Cycle 23 were substantially weaker than those produced during the previous cycles and those (weak) polar fields are the seeds for the activity of the following cycle. The polar fields are produced by the latitudinal transport of magnetic flux that emerged in low-latitude active regions. The polar fields thus depend upon the details of both the flux emergence and the flux transport. We have measured the flux transport flows (differential rotation, meridional flow, and supergranules) since 1996 and find systematic and substantial variation in the meridional flow alone. Here we present experiments using a Surface Flux Transport Model in which magnetic field data from SOHO/MDI and SDO/HMI are assimilated into the model only at latitudes between 45-degrees north and south of the equator (this assures that the details of the active region flux emergence are well represented). This flux is then transported in both longitude and latitude by the observed flows. In one experiment the meridional flow is given by the time averaged (and north-south symmetric) meridional flow profile. In the second experiment the time-varying and north-south asymmetric meridional flow is used. Differences between the observed polar fields and those produced in these two experiments allow us to ascertain the effects of these meridional flow variations on the Sun s polar fields.

  5. Active Pacific meridional overturning circulation (PMOC) during the warm Pliocene.

    Science.gov (United States)

    Burls, Natalie J; Fedorov, Alexey V; Sigman, Daniel M; Jaccard, Samuel L; Tiedemann, Ralf; Haug, Gerald H

    2017-09-01

    An essential element of modern ocean circulation and climate is the Atlantic meridional overturning circulation (AMOC), which includes deep-water formation in the subarctic North Atlantic. However, a comparable overturning circulation is absent in the Pacific, the world's largest ocean, where relatively fresh surface waters inhibit North Pacific deep convection. We present complementary measurement and modeling evidence that the warm, ~400-ppmv (parts per million by volume) CO 2 world of the Pliocene supported subarctic North Pacific deep-water formation and a Pacific meridional overturning circulation (PMOC) cell. In Pliocene subarctic North Pacific sediments, we report orbitally paced maxima in calcium carbonate accumulation rate, with accompanying pigment and total organic carbon measurements supporting deep-ocean ventilation-driven preservation as their cause. Together with high accumulation rates of biogenic opal, these findings require vigorous bidirectional communication between surface waters and interior waters down to ~3 km in the western subarctic North Pacific, implying deep convection. Redox-sensitive trace metal data provide further evidence of higher Pliocene deep-ocean ventilation before the 2.73-Ma (million years) transition. This observational analysis is supported by climate modeling results, demonstrating that atmospheric moisture transport changes, in response to the reduced meridional sea surface temperature gradients of the Pliocene, were capable of eroding the halocline, leading to deep-water formation in the western subarctic Pacific and a strong PMOC. This second Northern Hemisphere overturning cell has important implications for heat transport, the ocean/atmosphere cycle of carbon, and potentially the equilibrium response of the Pacific to global warming.

  6. ESTIMATING THE DEEP SOLAR MERIDIONAL CIRCULATION USING MAGNETIC OBSERVATIONS AND A DYNAMO MODEL: A VARIATIONAL APPROACH

    Energy Technology Data Exchange (ETDEWEB)

    Hung, Ching Pui; Jouve, Laurène; Brun, Allan Sacha [Laboratoire AIM Paris-Saclay, CEA/IRFU Université Paris-Diderot CNRS/INSU, F-91191 Gif-Sur-Yvette (France); Fournier, Alexandre [Institut de Physique du Globe de Paris, Sorbonne Paris Cité, Université Paris Diderot UMR 7154 CNRS, F-75005 Paris (France); Talagrand, Olivier [Laboratoire de météorologie dynamique, UMR 8539, Ecole Normale Supérieure, Paris Cedex 05 (France)

    2015-12-01

    We show how magnetic observations of the Sun can be used in conjunction with an axisymmetric flux-transport solar dynamo model in order to estimate the large-scale meridional circulation throughout the convection zone. Our innovative approach rests on variational data assimilation, whereby the distance between predictions and observations (measured by an objective function) is iteratively minimized by means of an optimization algorithm seeking the meridional flow that best accounts for the data. The minimization is performed using a quasi-Newton technique, which requires knowledge of the sensitivity of the objective function to the meridional flow. That sensitivity is efficiently computed via the integration of the adjoint flux-transport dynamo model. Closed-loop (also known as twin) experiments using synthetic data demonstrate the validity and accuracy of this technique for a variety of meridional flow configurations, ranging from unicellular and equatorially symmetric to multicellular and equatorially asymmetric. In this well-controlled synthetic context, we perform a systematic study of the behavior of our variational approach under different observational configurations by varying their spatial density, temporal density, and noise level, as well as the width of the assimilation window. We find that the method is remarkably robust, leading in most cases to a recovery of the true meridional flow to within better than 1%. These encouraging results are a first step toward using this technique to (i) better constrain the physical processes occurring inside the Sun and (ii) better predict solar activity on decadal timescales.

  7. Enthalpy screen of drug candidates.

    Science.gov (United States)

    Schön, Arne; Freire, Ernesto

    2016-11-15

    The enthalpic and entropic contributions to the binding affinity of drug candidates have been acknowledged to be important determinants of the quality of a drug molecule. These quantities, usually summarized in the thermodynamic signature, provide a rapid assessment of the forces that drive the binding of a ligand. Having access to the thermodynamic signature in the early stages of the drug discovery process will provide critical information towards the selection of the best drug candidates for development. In this paper, the Enthalpy Screen technique is presented. The enthalpy screen allows fast and accurate determination of the binding enthalpy for hundreds of ligands. As such, it appears to be ideally suited to aid in the ranking of the hundreds of hits that are usually identified after standard high throughput screening. Copyright © 2016 Elsevier Inc. All rights reserved.

  8. Inferences of the deep solar meridional flow

    Science.gov (United States)

    Böning, Vincent G. A.

    2017-10-01

    Understanding the solar meridional flow is important for uncovering the origin of the solar activity cycle. Yet, recent helioseismic estimates of this flow have come to conflicting conclusions in deeper layers of the solar interior, i.e., at depths below about 0.9 solar radii. The aim of this thesis is to contribute to a better understanding of the deep solar meridional flow. Time-distance helioseismology is the major method for investigating this flow. In this method, travel times of waves propagating between pairs of locations on the solar surface are measured. Until now, the travel-time measurements have been modeled using the ray approximation, which assumes that waves travel along infinitely thin ray paths between these locations. In contrast, the scattering of the full wave field in the solar interior due to the flow is modeled in first order by the Born approximation. It is in general a more accurate model of the physics in the solar interior. In a first step, an existing model for calculating the sensitivity of travel-time measurements to solar interior flows using the Born approximation is extended from Cartesian to spherical geometry. The results are succesfully compared to the Cartesian ones and are tested for self-consistency. In a second step, the newly developed model is validated using an existing numerical simulation of linear wave propagation in the Sun. An inversion of artificial travel times for meridional flow shows excellent agreement for noiseless data and reproduces many features in the input flow profile in the case of noisy data. Finally, the new method is used to infer the deep meridional flow. I used Global Oscillation Network Group (GONG) data that were earlier analyzed using the ray approximation and I employed the same Substractive Optimized Local Averaging (SOLA) inversion technique as in the earlier study. Using an existing formula for the covariance of travel-time measurements, it is shown that the assumption of uncorrelated errors

  9. Low-frequency variability of meridional transport in the divergence zone of the North Atlantic subtropical and subpolar gyres. The WOCE section A2; Niederfrequente Variabilitaet meridionaler Transporte in der Divergenzzone des nordatlantischen Subtropen- und Subpolarwirbels. Der WOCE-Schnitt A2

    Energy Technology Data Exchange (ETDEWEB)

    Lorbacher, K.

    2000-07-01

    The subinertial, climate relevant variability of the large-scale ocean circulation in the northern North Atlantic and its integral key parameters such as the advective transports of mass (volume), heat and freshwater are determined from observations alone using the hydrographic data from seven realisations of the so-called '48 N'-section between the English Channel and the Grand Banks of Newfoundland. The data consist of five available sets of the WOCE/A2-section during the Nineties for the years 1993, 1994, 1996, 1997, 1998 and of two previous transatlantic cruises in April of 1957 and 1982. The realisations of the WOCE/A2-section were carried out in the same season (May to July), except for the cruise in October 1994. The '48 N'-section follows the divergence zone of the mainly wind-driven subtropical gyre and the more complex, with respect to the forcing, subpolar gyre. In the central Westeuropean and Newfoundland Basins the section runs a few degrees south of the line of zero wind stress curl (curl{sub z}{tau}). In the West, the WOCE/A2-section turns northwest to cross the boundary current regime perpendicularly. Therefore, this quasi-zonal hydrographic section covers all large-scale circulation elements on the regional scale that contribute essentially to the ocean circulation on the global scale - the Meridional Overturning Circulation (MOC). The transport estimates are given as the sum of the three transport components of a quasi-steady, large-scale ocean circulation: The ageostrophic Ekman-, and the two geostrophic components, the depth-independent, barotropic or Sverdrup- and the baroclinic component. To maintain the mass balance over the plane of the section the compensation of each component is assumed. In the case of the baroclinic component the balance is achieved through a suitable choice for a surface of 'no-motion'. The absolute meridional velocity as a function of the zonal distance along the section and depth is

  10. Pulling the Meridional Overturning Circulation From the South DESC0005100

    Energy Technology Data Exchange (ETDEWEB)

    Cessi, Paola [Univ. of California, San Diego, CA (United States); Wolfe, Christopher L. [Scripps Inst. of Oceanography, San Diego, CA (United States)

    2015-11-25

    This project concerned the Atlantic Meridional Overturning Circulation (AMOC), its stability, variability and sensitivity to atmospheric forcing, both mechanical (wind-stress) and thermodynamical (heat and freshwater surface fluxes). The focus of the study is the interhemispheric cell in the largely adiabatic regime, where the flow is characterized by a descending branch in the high latitudes of the North Atlantic and the upwelling branch in the Antarctic Circumpolar Current (ACC) region of the Southern Ocean. These two end points are connected by shared isopycnals along which the flow takes place. The approach is to systematically study the amplitude and frequency of the AMOC’s response to localized buoyancy with an ocean-only model in both coarse and high-resolution configurations, analyzed with innovative diagnostics, focused on the “residual overturning circulation” (ROC), which is the proper measure of the transport of heat and other tracers.

  11. Enthalpy of formation of zircon

    International Nuclear Information System (INIS)

    Ellison, A.J.G.; Navrotsky, A.

    1992-01-01

    Using high-temperature solution calorimetry in molt 2PbO · B 2 O 3 , the enthalpy of reaction of the formation of zircon, ZrSiO 4 , from its constituent oxides has been determined: Δ 4 H 977 (ZrSiO 4 ) = -27.9 (±1.9) kJ/mol. With previously reported data for the heat contents of ZrO 2 SiO 2 and ZrSiO 4 and standard-state enthalpies of formation of ZrO 2 and SiO 2 , we obtain Δ f H 298 degrees. (ZrSiO 4 ) = -2034.2 (±3.1) kJ/mol and Δ t G 298 degrees (ZrSiO 4 ) = -1919.8 kJ/mol. The free energy value is in excellent agreement with a range previously estimated from solid-state reaction equilibria. At higher temperature also the data are in close agreement with existing data, though the data sets diverge somewhat with increasing T. In this paper the limitations of the data for predicting the breakdown temperature of zircon into its constituent oxides are discussed

  12. Currents, Geostrophic, Aviso, 0.25 degrees, Global, Meridional

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Aviso Meridional Geostrophic Current is inferred from Sea Surface Height Deviation, climatological dynamic height, and basic fluid mechanics.

  13. North Pacific Meridional Mode over the Common Era

    Science.gov (United States)

    Sanchez, S. C.; Charles, C. D.; Amaya, D. J.; Miller, A. J.

    2016-12-01

    The Pacific Meridional Mode (PMM) has been increasingly recognized as an influential mode of variability for channeling extratropical anomalies to the equatorial ocean-atmosphere system. The PMM has been identified as an important precursor for ENSO, a source of much decadal power in the tropical Pacific, and is potentially intensifying. It is still unknown why the Pacific Meridional Mode might be intensifying; most arguments center around the changing mean state associated with anthropogenic global warming. There are a number of processes by which the background state could influence the PMM: altering the location of trade winds, the characteristics of stochastic forcing, the sensitivity of latent heat flux to surface wind anomalies, the wind response to SST anomalies, or changing the Intertropical Convergence Zone (ITCZ) structure. Recent work has found that the PMM is particularly sensitive to ITCZ shifts in intensity and location (using a simple linear coupled model, [Martinez-Villalobos and Vimont 2016]). Over the last millennium the ITCZ has experienced epochs of notable latitudinal shifts to balance the cross equatorial energy transport. Here we investigate how the strength of the PMM may have varied with these shifts in the ITCZ over the Common Era using the CESM-Last Millennium Ensemble (LME). We assess the strength of the PMM pathway by the degree of air-sea coupling and the amplitude of tropical decadal variability. We expect the ITCZ location and the degree of air-sea coupling (WES feedback) to play a critical role in determining the effectiveness and intensity of the PMM pathway. We verify our inferences in the LME with coral paleoproxy records from the central tropical Pacific. Chiefly we target records from the Line Islands (spanning 1°N to 6°N) to infer variations in the location of the ITCZ and the amplitude of decadal variability. This work enables us to discuss the idea of an intensifying PMM in a more historical context.

  14. Modelling of high-enthalpy, high-Mach number flows

    International Nuclear Information System (INIS)

    Degrez, G; Lani, A; Panesi, M; Chazot, O; Deconinck, H

    2009-01-01

    A review is made of the computational models of high-enthalpy flows developed over the past few years at the von Karman Institute and Universite Libre de Bruxelles, for the modelling of high-enthalpy hypersonic (re-)entry flows. Both flows in local thermo-chemical equilibrium (LTE) and flows in thermo-chemical non-equilibrium (TCNEQ) are considered. First, the physico-chemical models are described, i.e. the set of conservation laws, the thermodynamics, transport phenomena and chemical kinetics models. Particular attention is given to the correct modelling of elemental (LTE flows) and species (chemical non-equilibrium-CNEQ-flows) transport. The numerical algorithm, based on a state-of-the-art finite volume discretization, is then briefly described. Finally, selected examples are included to illustrate the capabilities of the developed solver. (review article)

  15. Intraseasonal meridional current variability in the eastern equatorial Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Ogata, T.; Sasaki, H.; Murty, V.S.N.; Sarma, M.S.S.; Masumoto, Y.

    values of the Mixed Rossby-gravity wave at 15-d period. This meridional current variability shows large coherence with the local meridional wind stress, suggesting the upper-ocean responses to the local wind-forcing. A part of the energy of the biweekly...

  16. Causes and impacts of changes in the stratospheric meridional circulation in a chemistry-climate model

    Energy Technology Data Exchange (ETDEWEB)

    Garny, Hella

    2011-05-13

    The stratospheric meridional circulation is projected to be subject to changes due to enhanced greenhouse-gas concentrations in the atmosphere. This study aims to diagnose and explain long-term changes in the stratospheric meridional circulation using the chemistry-climate model E39CA. The diagnosed strengthening of the circulation is found to be driven by increases in tropical sea surface temperatures which lead to a strengthening and upward shift of the subtropical jets. This enables enhanced vertical propagation of large scale waves into the lower stratosphere, and therefore stronger local wave forcing of the meridional circulation in the tropical lower stratosphere. The impact of changes in transport on the ozone layer is analysed using a newly developed method that allows the separation of the effects of transport and chemistry changes on ozone. It is found that future changes of mean stratospheric ozone concentrations are largely determined by changes in chemistry, while changes in transport of ozone play a minor role. (orig.)

  17. Polymer-Polymer Miscibility and Enthalpy Relaxations

    NARCIS (Netherlands)

    Bosma, Martin; Brinke, Gerrit ten; Ellis, Thomas S.

    Annealing of polymers below the glass transition temperature results in a decrease in enthalpy that is recovered during heating. The enthalpy recovery is visible as an endothermic peak in a differential scanning calorimetry (DSC) scan. The position of this peak depends on the thermal treatment given

  18. Anomalous enthalpy relaxation in vitreous silica

    DEFF Research Database (Denmark)

    Yue, Yuanzheng

    2015-01-01

    scans. It is known that the liquid fragility (i.e., the speed of the viscous slow-down of a supercooled liquid at its Tg during cooling) has impact on enthalpy relaxation in glass. Here, we find that vitreous silica (as a strong system) exhibits striking anomalies in both glass transition and enthalpy...

  19. Enthalpy damping for the steady Euler equations

    Science.gov (United States)

    Jespersen, D. C.

    1985-01-01

    For inviscid steady flow problems where the enthalpy is constant at steady state, it was previously proposed to use the difference between the local enthalpy and the steady state enthalpy as a driving term to accelerate convergence of iterative schemes. This idea is analyzed, both on the level of the partial differential equation and on the level of a particular finite difference scheme. It is shown that for the two-dimensional unsteady Euler equations, a hyperbolic system with eigenvalues on the imaginary axis, there is no enthalpy damping strategy which moves all the eigenvalues into the open left half plane. For the numerical scheme, however, the analysis shows and examples verify that enthalpy damping is potentially effective in accelerating convergence to steady state.

  20. Three-pattern decomposition of global atmospheric circulation: part II—dynamical equations of horizontal, meridional and zonal circulations

    Science.gov (United States)

    Hu, Shujuan; Cheng, Jianbo; Xu, Ming; Chou, Jifan

    2018-04-01

    The three-pattern decomposition of global atmospheric circulation (TPDGAC) partitions three-dimensional (3D) atmospheric circulation into horizontal, meridional and zonal components to study the 3D structures of global atmospheric circulation. This paper incorporates the three-pattern decomposition model (TPDM) into primitive equations of atmospheric dynamics and establishes a new set of dynamical equations of the horizontal, meridional and zonal circulations in which the operator properties are studied and energy conservation laws are preserved, as in the primitive equations. The physical significance of the newly established equations is demonstrated. Our findings reveal that the new equations are essentially the 3D vorticity equations of atmosphere and that the time evolution rules of the horizontal, meridional and zonal circulations can be described from the perspective of 3D vorticity evolution. The new set of dynamical equations includes decomposed expressions that can be used to explore the source terms of large-scale atmospheric circulation variations. A simplified model is presented to demonstrate the potential applications of the new equations for studying the dynamics of the Rossby, Hadley and Walker circulations. The model shows that the horizontal air temperature anomaly gradient (ATAG) induces changes in meridional and zonal circulations and promotes the baroclinic evolution of the horizontal circulation. The simplified model also indicates that the absolute vorticity of the horizontal circulation is not conserved, and its changes can be described by changes in the vertical vorticities of the meridional and zonal circulations. Moreover, the thermodynamic equation shows that the induced meridional and zonal circulations and advection transport by the horizontal circulation in turn cause a redistribution of the air temperature. The simplified model reveals the fundamental rules between the evolution of the air temperature and the horizontal, meridional

  1. Undergraduate Students' Conceptions of Enthalpy, Enthalpy Change and Related Concepts

    Science.gov (United States)

    Nilsson, Tor; Niedderer, Hans

    2014-01-01

    Research shows that students have problems understanding thermodynamic concepts and that a gap exists at the tertiary level related to more specific chemistry concepts such as enthalpy. Therefore, the aim of this study is to construct undergraduate students' conceptions of enthalpy, its change and related concepts. Three explorative small-scale…

  2. Interannual Variability of the Meridional Width of the Baiu Rainband in June and the Associated Large-Scale Atmospheric Circulations

    Science.gov (United States)

    Tsuji, K.; Tomita, T.

    2016-12-01

    part of the North Pacific subtropical high. This anomalous anticyclone (cyclone) enhances (reduces) the moisture transport from Southeast Asia to Japan and biases the southern edge of baiu rainband northward (southward). Thus, the meridional width of baiu rainband has the interannual variability.

  3. Free enthalpy landscape of SrO.

    Science.gov (United States)

    Schön, J C; Cancarević, Z P; Hannemann, A; Jansen, M

    2008-05-21

    Trying to predict thermodynamically stable and metastable solid compounds as function of pressure and temperature requires the global exploration of the enthalpy landscapes of chemical systems and the subsequent construction of their free enthalpy landscapes. In this work, we present a general approach to the determination of a free energy landscape. As an example, we construct the free enthalpy landscape of SrO for two different pressures on the empirical potential level and also compute various thermodynamic and elastic properties of SrO in the NaCl-, CsCl-, NiAs-, NbS-, TiP-, beta-BeO, sphalerite-, and wurtzite-structure type on an ab initio level. We employ density functional theory within the hybrid B3LYP approximation. The results show good agreement with experimental and theoretical data.

  4. Enthalpy relaxation and annealing effect in polystyrene.

    Science.gov (United States)

    Sakatsuji, Waki; Konishi, Takashi; Miyamoto, Yoshihisa

    2013-07-01

    The effects of thermal history on the enthalpy relaxation in polystyrene are studied by differential scanning calorimetry. The temperature dependence of the specific heat in the liquid and the glassy states, that of relaxation time, and the exponent of the Kohlrausch-Williams-Watts function are determined by measurements of the thermal response against sinusoidal temperature variation. A phenomenological model equation previously proposed to interpret the memory effect in the frozen state is applied to the enthalpy relaxation and the evolution of entropy under a given thermal history is calculated. The annealing below the glass transition temperature produces two effects on enthalpy relaxation: the decay of excess entropy with annealing time in the early stage of annealing and the increase in relaxation time due to physical aging in the later stage. The crossover of these effects is reflected in the variation of temperature of the maximum specific heat observed in the heating process after annealing and cooling.

  5. Standard enthalpies of formation of uranium compounds

    International Nuclear Information System (INIS)

    Cordfunke, E.H.P.; Ouweltjes, W.

    1977-01-01

    Enthalpies of solution of β-UO 2 SO 4 and α-UO 2 SeO 4 in H 2 SO 4 (aq) and of UO 2 SeO 3 in H 2 SO 4 (aq) + Ce(SO 4 ) 2 have been measured calorimetrically. Together with measurements of the enthalpy of solution of γ-UO 3 in these solvents, the standard enthalpies of formation of anhydrous β-UO 2 SO 4 , α-UO 2 SeO 4 , and UO 2 SeO 3 have been derived. The results obtained are: ΔHsub(f) 0 (s, 298.15 K)/ kcalsub(th) mol -1 : β-UO 2 SO 4 , -(440.9 +- 0.2); α-UO 2 SeO 4 , -(367.9 +- 0.8); UO 2 SeO 3 , -(363.8 +- 0.2). (author)

  6. Case study of enthalpy-entropy noncompensation

    Science.gov (United States)

    Graziano, Giuseppe

    2004-03-01

    Enthalpy-entropy noncompensation characterizes the relative changes in the hydration thermodynamic functions upon "transforming" ethane into fluoromethane, chloromethane, bromomethane, and iodomethane. An analysis grounded on a simple statistical mechanical theory of hydration allows a plausible rationalization of such enthalpy-entropy noncompensation. It is shown that increasing the strength of solute-water attractive interactions modifying the chemical nature of a part of the solute molecule, but not its size, is a largely noncompensating process for the hydration of noncharged and nonhydrogen bonding species, and dominates the compensating contribution coming from the reorganization of water H bonds.

  7. Recommended sublimation pressure and enthalpy of benzene

    Czech Academy of Sciences Publication Activity Database

    Růžička, K.; Fulem, Michal; Červinka, C.

    2014-01-01

    Roč. 68, Jan (2014), s. 40-47 ISSN 0021-9614 Institutional support: RVO:68378271 Keywords : benzene * vapor pressure * heat capacity * ideal-gas thermodynamic properties * sublimation enthalpy * recommended vapor pressure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.679, year: 2014

  8. The Optimal Use of Entropy and Enthalpy

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 6; Issue 9. The Optimal Use of Entropy and Enthalpy. M S Ananth R Ravi. General Article Volume 6 Issue 9 September 2001 pp 67-81. Fulltext. Click here to view fulltext PDF. Permanent link: http://www.ias.ac.in/article/fulltext/reso/006/09/0067-0081 ...

  9. AIRS observations of seasonal variability in meridional temperature ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Earth System Science; Volume 122; Issue 1. AIRS observations of seasonal variability in meridional temperature gradient over Indian region at 100 hPa. A Gupta S K Dhaka V Panwar R Bhatnagar V Kumar Savita M Datta S K Dash. Volume 122 Issue 1 February 2013 pp 201-213 ...

  10. Link between convection and meridional gradient of sea surface ...

    Indian Academy of Sciences (India)

    . Resolution. URL. SST. TMI ... In this paper, we use satellite data for SST and rainfall to show that there exists a strong relationship between convec- tion and the meridional gradient of SST in the bay. We show that convection sets in within a ...

  11. AIRS observations of seasonal variability in meridional temperature ...

    Indian Academy of Sciences (India)

    Meridional temperature gradient; Atmospheric Infra Red Sounder (AIRS) data; Indian summer monsoon; .... fine scale earlier in this region, due to paucity of data. 2. Data. We have used AIRS (AIRX3STM) version 5 level. 3 research quality product (http://airs.jpl.nasa. ..... regional information as we are presenting in this.

  12. Dynamics of the global meridional ice flow of Europa's icy shell

    Science.gov (United States)

    Ashkenazy, Yosef; Sayag, Roiy; Tziperman, Eli

    2018-01-01

    Europa is one of the most probable places in the solar system to find extra-terrestrial life1,2, motivating the study of its deep ( 100 km) ocean3-6 and thick icy shell3,7-11. The chaotic terrain patterns on Europa's surface12-15 have been associated with vertical convective motions within the ice8,10. Horizontal gradients of ice thickness16,17 are expected due to the large equator-to-pole gradient of surface temperature and can drive a global horizontal ice flow, yet such a flow and its observable implications have not been studied. We present a global ice flow model for Europa composed of warm, soft ice flowing beneath a cold brittle rigid ice crust3. The model is coupled to an underlying (diffusive) ocean and includes the effect of tidal heating and convection within the ice. We show that Europa's ice can flow meridionally due to pressure gradients associated with equator-to-pole ice thickness differences, which can be up to a few km and can be reduced both by ice flow and due to ocean heat transport. The ice thickness and meridional flow direction depend on whether the ice convects or not; multiple (convecting and non-convecting) equilibria are found. Measurements of the ice thickness and surface temperature from future Europa missions18,19 can be used with our model to deduce whether Europa's icy shell convects and to constrain the effectiveness of ocean heat transport.

  13. Calibration models for high enthalpy calorimetric probes.

    Science.gov (United States)

    Kannel, A

    1978-07-01

    The accuracy of gas-aspirated liquid-cooled calorimetric probes used for measuring the enthalpy of high-temperature gas streams is studied. The error in the differential temperature measurements caused by internal and external heat transfer interactions is considered and quantified by mathematical models. The analysis suggests calibration methods for the evaluation of dimensionless heat transfer parameters in the models, which then can give a more accurate value for the enthalpy of the sample. Calibration models for four types of calorimeters are applied to results from the literature and from our own experiments: a circular slit calorimeter developed by the author, single-cooling jacket probe, double-cooling jacket probe, and split-flow cooling jacket probe. The results show that the models are useful for describing and correcting the temperature measurements.

  14. Experimental evaluation of enthalpy efficiency and gas-phase contaminant transfer in an enthalpy recovery unit with polymer membrane foils

    DEFF Research Database (Denmark)

    Nie, Jinzhe; Yang, Jianrong; Fang, Lei

    2015-01-01

    Experimental studies were conducted in a laboratory setting to investigate the enthalpy efficiency and gas-phase contaminant transfer in a polymer membrane enthalpy recovery unit. One commercially available polymer membrane enthalpy recovery unit was used as a reference unit. Simulated indoor air...

  15. Active Pacific meridional overturning circulation (PMOC) during the warm Pliocene

    OpenAIRE

    Burls, Natalie J.; Fedorov, Alexey V.; Sigman, Daniel M.; Jaccard, Samuel L.; Tiedemann, Ralf; Haug, Gerald H.

    2017-01-01

    An essential element of modern ocean circulation and climate is the Atlantic meridional overturning circulation (AMOC), which includes deep-water formation in the subarctic North Atlantic. However, a comparable overturning circulation is absent in the Pacific, theworld's largest ocean, where relatively fresh surface waters inhibitNorth Pacific deep convection. We present complementary measurement and modeling evidence that the warm, similar to 400-ppmv (parts per million by volume) CO2 world ...

  16. Application of low enthalpy geothermal energy

    International Nuclear Information System (INIS)

    Stancher, B.; Giannone, G.

    2007-01-01

    Geothermal energy comes from the superficial layers of the Earth's crust; it can be exploited in several ways, depending on its temperature. Many systems have been developed to use this clean and renewable energy resource. This paper deals with a particular application of low enthalpy geothermal energy in Latisana (district of Udine NE, Italy). The Latisana's indoor stadium is equipped with geothermal plant that uses low temperature water (29-30 0 ) to provide heating. Economic analysis shows that the cost of its plant is comparable to the cost powered by other kinds of renewable energy resources

  17. Meridional overturning circulation conveys fast acidification to the deep Atlantic Ocean

    Science.gov (United States)

    Perez, Fiz F.; Fontela, Marcos; García-Ibáñez, Maribel I.; Mercier, Herlé; Velo, Anton; Lherminier, Pascale; Zunino, Patricia; de La Paz, Mercedes; Alonso-Pérez, Fernando; Guallart, Elisa F.; Padin, Xose A.

    2018-02-01

    Since the Industrial Revolution, the North Atlantic Ocean has been accumulating anthropogenic carbon dioxide (CO2) and experiencing ocean acidification, that is, an increase in the concentration of hydrogen ions (a reduction in pH) and a reduction in the concentration of carbonate ions. The latter causes the ‘aragonite saturation horizon’—below which waters are undersaturated with respect to a particular calcium carbonate, aragonite—to move to shallower depths (to shoal), exposing corals to corrosive waters. Here we use a database analysis to show that the present rate of supply of acidified waters to the deep Atlantic could cause the aragonite saturation horizon to shoal by 1,000-1,700 metres in the subpolar North Atlantic within the next three decades. We find that, during 1991-2016, a decrease in the concentration of carbonate ions in the Irminger Sea caused the aragonite saturation horizon to shoal by about 10-15 metres per year, and the volume of aragonite-saturated waters to reduce concomitantly. Our determination of the transport of the excess of carbonate over aragonite saturation (xc[CO32-])—an indicator of the availability of aragonite to organisms—by the Atlantic meridional overturning circulation shows that the present-day transport of carbonate ions towards the deep ocean is about 44 per cent lower than it was in preindustrial times. We infer that a doubling of atmospheric anthropogenic CO2 levels—which could occur within three decades according to a ‘business-as-usual scenario’ for climate change—could reduce the transport of xc[CO32-] by 64-79 per cent of that in preindustrial times, which could severely endanger cold-water coral habitats. The Atlantic meridional overturning circulation would also export this acidified deep water southwards, spreading corrosive waters to the world ocean.

  18. OCEAN CIRCULATION. Observing the Atlantic Meridional Overturning Circulation yields a decade of inevitable surprises.

    Science.gov (United States)

    Srokosz, M A; Bryden, H L

    2015-06-19

    The importance of the Atlantic Meridional Overturning Circulation (AMOC) heat transport for climate is well acknowledged. Climate models predict that the AMOC will slow down under global warming, with substantial impacts, but measurements of ocean circulation have been inadequate to evaluate these predictions. Observations over the past decade have changed that situation, providing a detailed picture of variations in the AMOC. These observations reveal a surprising degree of AMOC variability in terms of the intraannual range, the amplitude and phase of the seasonal cycle, the interannual changes in strength affecting the ocean heat content, and the decline of the AMOC over the decade, both of the latter two exceeding the variations seen in climate models. Copyright © 2015, American Association for the Advancement of Science.

  19. Tailoring Meridional and Seasonal Radiative Forcing by Sulfate Aerosol Solar Geoengineering

    Science.gov (United States)

    Dai, Z.; Weisenstein, D. K.; Keith, D. W.

    2018-01-01

    We study the possibility of designing solar radiation management schemes to achieve a desired meridional radiative forcing (RF) profile using a two-dimensional chemistry-transport-aerosol model. Varying SO2 or H2SO4 injection latitude, altitude, and season, we compute RF response functions for a broad range of possible injection schemes, finding that linear combinations of these injection cases can roughly achieve RF profiles that have been proposed to accomplish various climate objectives. Globally averaged RF normalized by the sulfur injection rate (the radiative efficacy) is largest for injections at high altitudes, near the equator, and using emission of H2SO4 vapor into an aircraft wake to produce accumulation-mode particles. There is a trade-off between radiative efficacy and control as temporal and spatial control is best achieved with injections at lower altitudes and higher latitudes. These results may inform studies using more realistic models that couple aerosol microphysics, chemistry, and stratospheric dynamics.

  20. Enthalpy?entropy compensation: the role of solvation

    OpenAIRE

    Dragan, Anatoliy I.; Read, Christopher M.; Crane-Robinson, Colyn

    2016-01-01

    Structural modifications to interacting systems frequently lead to changes in both the enthalpy (heat) and entropy of the process that compensate each other, so that the Gibbs free energy is little changed: a major barrier to the development of lead compounds in drug discovery. The conventional explanation for such enthalpy-entropy compensation (EEC) is that tighter contacts lead to a more negative enthalpy but increased molecular constraints, i.e. a compensating conformational entropy reduct...

  1. Formation enthalpy of binary magnesium, cesium selenates

    International Nuclear Information System (INIS)

    Selivanova, N.M.; Prymova, L.A.

    1975-01-01

    As a result of dehydration of schoenite, Cs 2 Mg(SeO 4 ) 2 x6H 2 O, the following compounds have been obtained: Cs 2 Mg(SeO 4 ) 2 x4H 2 O, Cs 2 Mg(SeO 4 ) 2 x2H 2 O and Cs 2 Mg(SeO 4 ) 2 . The standard enthalpies of formation from simple compounds have been determinated by calorimetric measurements: Cs 2 Mg(SeO 4 ) 2 x4H 2 O - ΔH deg 298 = -797.5+-0.9 kcal/mol; Cs 2 Mg(SeO 4 ) 2 x2H 2 O - ΔH deg 298 = -657.5+-0.9 kcal/mol; and Cs 2 Mg(SeO 4 ) 2 cryst - ΔH deg 298 = -507.0+-1.0 kcal/mol

  2. Enthalpy: A Metaphor for a Design Guide for Conversations.

    Science.gov (United States)

    Dyer, Gordon

    1996-01-01

    Provides insights into the design of effective educational planning conversations derived from the metaphor of enthalpy (the amount of heat energy released when chemical reactions occur). Interprets enthalpy changes in the context of energy and the dynamics necessary to sustain an effective systems design conversation. (AEF)

  3. Enthalpy of Vaporization by Gas Chromatography: A Physical Chemistry Experiment

    Science.gov (United States)

    Ellison, Herbert R.

    2005-01-01

    An experiment is conducted to measure the enthalpy of vaporization of volatile compounds like methylene chloride, carbon tetrachloride, and others by using gas chromatography. This physical property was measured using a very tiny quantity of sample revealing that it is possible to measure the enthalpies of two or more compounds at the same time.

  4. Enthalpy of mixing of liquid Co–Sn alloys

    International Nuclear Information System (INIS)

    Yakymovych, A.; Fürtauer, S.; Elmahfoudi, A.; Ipser, H.; Flandorfer, H.

    2014-01-01

    Highlights: • The enthalpies of mixing of liquid Co–Sn alloys between T = (673 and 1773) K. • The temperature dependence of the enthalpies of mixing was described. • Full report of measured values including polynomial coefficients. - Abstract: A literature overview of enthalpy of mixing data for liquid Co–Sn alloys shows large scattering but no clear temperature dependence. Therefore drop calorimetry was performed in the Co–Sn system at twelve different temperatures in 100 K steps in the temperature range (673 to 1773) K. The integral enthalpy of mixing was determined starting from 1173 K and fitted to a standard Redlich–Kister polynomial. In addition, the limiting partial molar enthalpy of Co in Sn was investigated by small additions of Co to liquid Sn at temperatures (673 to 1773) K. The integral and partial molar enthalpies of the Co–Sn system generally show an exothermic mixing behavior. Significant temperature dependence was detected for the enthalpies of mixing. The minimum integral enthalpy values vary with rising temperature from approx. −7820 J/mol at T = 1173 K to −1350 J/mol at T = 1773 K; the position of the minimum is between (59 and 61) at.% Co. The results are discussed and compared with literature data available for this system. X-ray studies and scanning electron microscopy of selected alloys obtained from the calorimetric measurements were carried out in order to check the completeness of the solution process

  5. Enthalpy-entropy compensation and the isokinetic temperature in ...

    Indian Academy of Sciences (India)

    Enthalpy-entropy compensation supposes that differences in activation enthalpy delta-H-++ for different reactions (or, typically inbiochemistry, the same reaction catalysed by enzymes obtained from different species) may be compensated for bydifferences in activation entropy delta-S-++. At the isokinetic temperature the ...

  6. Enthalpy of solution of rubidium nitrate in water

    International Nuclear Information System (INIS)

    Weintraub, R.; Apelblat, A.; Tamir, A.

    1984-01-01

    Molar enthalpies of solution of RbNO 3 in water at 298.15 K were measured in an LKB calorimeter. The molar enthalpies of solution extrapolated to infinite solution are: (36788 +- 30)J. mol -1 (Alfa) and (36539 +- 52)J.mol -1 (Aldrich). (author)

  7. Los testimonios de Marte en la Meseta Meridional

    Directory of Open Access Journals (Sweden)

    Julián Hurtado Aguña

    2001-01-01

    Full Text Available Marte, fue una de las más importantes divinidades romanas presentes en Híspanla. Dentro de la Meseta meridional sus testimonios aparecen en algunas localidades de la provincia de Madrid, como Alcalá de Henares, Talamanca del Jarama o Collado Villalba, estando ausentes en otras partes de esta región. Especialmente importante es la presencia de inscripciones dedicadas a Marte en la ciudad romana de Complutum (Alcalá de Henares, donde sus dedicantes pudieran pertenecer en algún caso al grupo social de los libertos.One oí the most important román divinities in Híspanla was Mars. His testimonies in the Meridional Plateau are in some villages of Madrid's province, as Alcalá de Henares, Talamanca del Jarama or Collado Villalba, and they are not in other places of this reglan. Specially important is ttie presence of inscriptions to Mars in ttie román town of Complutum (Alcalá de Henares, wtiere his devotes could belong to the social freedmans group.

  8. Structural parameterization of the binding enthalpy of small ligands.

    Science.gov (United States)

    Luque, Irene; Freire, Ernesto

    2002-11-01

    A major goal in ligand and drug design is the optimization of the binding affinity of selected lead molecules. However, the binding affinity is defined by the free energy of binding, which, in turn, is determined by the enthalpy and entropy changes. Because the binding enthalpy is the term that predominantly reflects the strength of the interactions of the ligand with its target relative to those with the solvent, it is desirable to develop ways of predicting enthalpy changes from structural considerations. The application of structure/enthalpy correlations derived from protein stability data has yielded inconsistent results when applied to small ligands of pharmaceutical interest (MW the enthalpy associated with any possible conformational change in the protein or ligand upon binding; and, (3) the enthalpy associated with protonation/deprotonation events, if present. As in the case of protein stability, the intrinsic binding enthalpy scales with changes in solvent accessible surface areas. However, an accurate estimation of the intrinsic binding enthalpy requires explicit consideration of long-lived water molecules at the binding interface. The best statistical structure/enthalpy correlation is obtained when buried water molecules within 5-7 A of the ligand are included in the calculations. For all seven protein systems considered (HIV-1 protease, dihydrodipicolinate reductase, Rnase T1, streptavidin, pp60c-Src SH2 domain, Hsp90 molecular chaperone, and bovine beta-trypsin) the binding enthalpy of 25 small molecular weight peptide and nonpeptide ligands can be accounted for with a standard error of +/-0.3 kcal x mol(-1). Copyright 2002 Wiley-Liss, Inc.

  9. Observed decline of the Atlantic Meridional Overturning circulation 2004 to 2012

    Science.gov (United States)

    Cunningham, Stuart; Smeed, David; Johns, William; Meinen, Chris; Rayner, Darren; Moat, Ben; Duchez, Aurelie; Bryden, Harry; Baringer Molly, O.; McCarthy, Gerard

    2014-05-01

    The Atlantic Meridional Overturning Circulation (AMOC) has been observed continuously at 26° N since April 2004. The AMOC and its component parts are monitored by combining a transatlantic array of moored instruments with submarine-cable based measurements of the Gulf Stream and satellite derived Ekman transport. The time series has recently been extended to October 2012 and the results show a downward trend since 2004. From April~2008 to March 2012 the AMOC was an average of 2.7 Sv weaker than in the first four years of observation (95% confidence that the reduction is 0.3 Sv or more). Ekman transport reduced by about 0.2 Sv and the Gulf Stream by 0.5 Sv but most of the change (2.0 Sv) is due to the mid-ocean geostrophic flow. The change of the mid-ocean geostrophic flow represents a strengthening of the subtropical gyre above the thermocline. The increased southward flow of warm waters is balanced by a decrease in the southward flow of Lower North Atlantic Deep Water below 3000 m. The transport of Lower North Atlantic Deep Water slowed by 7% per year (95% confidence that the rate of slowing is greater than 2.5% per year).

  10. Free enthalpies of replacing water molecules in protein binding pockets.

    Science.gov (United States)

    Riniker, Sereina; Barandun, Luzi J; Diederich, François; Krämer, Oliver; Steffen, Andreas; van Gunsteren, Wilfred F

    2012-12-01

    Water molecules in the binding pocket of a protein and their role in ligand binding have increasingly raised interest in recent years. Displacement of such water molecules by ligand atoms can be either favourable or unfavourable for ligand binding depending on the change in free enthalpy. In this study, we investigate the displacement of water molecules by an apolar probe in the binding pocket of two proteins, cyclin-dependent kinase 2 and tRNA-guanine transglycosylase, using the method of enveloping distribution sampling (EDS) to obtain free enthalpy differences. In both cases, a ligand core is placed inside the respective pocket and the remaining water molecules are converted to apolar probes, both individually and in pairs. The free enthalpy difference between a water molecule and a CH(3) group at the same location in the pocket in comparison to their presence in bulk solution calculated from EDS molecular dynamics simulations corresponds to the binding free enthalpy of CH(3) at this location. From the free enthalpy difference and the enthalpy difference, the entropic contribution of the displacement can be obtained too. The overlay of the resulting occupancy volumes of the water molecules with crystal structures of analogous ligands shows qualitative correlation between experimentally measured inhibition constants and the calculated free enthalpy differences. Thus, such an EDS analysis of the water molecules in the binding pocket may give valuable insight for potency optimization in drug design.

  11. A finite volume code for meridional circulation in stars

    CERN Document Server

    Talon, S; Michaud, G; Richer, J

    2003-01-01

    To understand the driving of both meridional circulation and differential rotation in radiative envelopes of stars, one has to solve for 3D mass, momentum, and energy conservation equations for a compressible gas in a central gravity field. In this study, we propose a novel finite volume technique that uses Cartesian geometry thus reducing greatly the complexity of spherical operators. The boundary conditions are efficiently imposed at the surface of the star using the fictitious points technique. We use the anelastic approximation and the Poisson equation for pressure is solved by the Jacobi method which preserves natural symmetries. We present analytical test cases of the fictitious domain technique, and show our results of asymptotic circulation in a model with little stratification and a large viscosity.

  12. On the stability of the Atlantic meridional overturning circulation

    Science.gov (United States)

    Hofmann, Matthias; Rahmstorf, Stefan

    2009-01-01

    One of the most important large-scale ocean current systems for Earth's climate is the Atlantic meridional overturning circulation (AMOC). Here we review its stability properties and present new model simulations to study the AMOC's hysteresis response to freshwater perturbations. We employ seven different versions of an Ocean General Circulation Model by using a highly accurate tracer advection scheme, which minimizes the problem of numerical diffusion. We find that a characteristic freshwater hysteresis also exists in the predominantly wind-driven, low-diffusion limit of the AMOC. However, the shape of the hysteresis changes, indicating that a convective instability rather than the advective Stommel feedback plays a dominant role. We show that model errors in the mean climate can make the hysteresis disappear, and we investigate how model innovations over the past two decades, like new parameterizations and mixing schemes, affect the AMOC stability. Finally, we discuss evidence that current climate models systematically overestimate the stability of the AMOC. PMID:19897722

  13. Predicting the enthalpies of melting and vaporization for pure components

    Science.gov (United States)

    Esina, Z. N.; Korchuganova, M. R.

    2014-12-01

    A mathematical model of the melting and vaporization enthalpies of organic components based on the theory of thermodynamic similarity is proposed. In this empirical model, the phase transition enthalpy for the homological series of n-alkanes, carboxylic acids, n-alcohols, glycols, and glycol ethers is presented as a function of the molecular mass, the number of carbon atoms in a molecule, and the normal transition temperature. The model also uses a critical or triple point temperature. It is shown that the results from predicting the melting and vaporization enthalpies enable the calculation of binary phase diagrams.

  14. Influence of glacial ice sheets on the Atlantic meridional overturning circulation through surface wind change

    Science.gov (United States)

    Sherriff-Tadano, Sam; Abe-Ouchi, Ayako; Yoshimori, Masakazu; Oka, Akira; Chan, Wing-Le

    2018-04-01

    Coupled modeling studies have recently shown that the existence of the glacial ice sheets intensifies the Atlantic meridional overturning circulation (AMOC). However, most models show a strong AMOC in their simulations of the Last Glacial Maximum (LGM), which is biased compared to reconstructions that indicate both a weaker and stronger AMOC during the LGM. Therefore, a detailed investigation of the mechanism behind this intensification of the AMOC is important for a better understanding of the glacial climate and the LGM AMOC. Here, various numerical simulations are conducted to focus on the effect of wind changes due to glacial ice sheets on the AMOC and the crucial region where the wind modifies the AMOC. First, from atmospheric general circulation model experiments, the effect of glacial ice sheets on the surface wind is evaluated. Second, from ocean general circulation model experiments, the influence of the wind stress change on the AMOC is evaluated by applying wind stress anomalies regionally or at different magnitudes as a boundary condition. These experiments demonstrate that glacial ice sheets intensify the AMOC through an increase in the wind stress at the North Atlantic mid-latitudes, which is induced by the North American ice sheet. This intensification of the AMOC is caused by the increased oceanic horizontal and vertical transport of salt, while the change in sea ice transport has an opposite, though minor, effect. Experiments further show that the Eurasian ice sheet intensifies the AMOC by directly affecting the deep-water formation in the Norwegian Sea.

  15. Enthalpy of Formation of N2H4(Hydrazine) Revisited.

    Science.gov (United States)

    Feller, David; Bross, David H; Ruscic, Branko

    2017-08-17

    In order to address the accuracy of the long-standing experimental enthalpy of formation of gas-phase hydrazine, fully confirmed in earlier versions of Active Thermochemical Tables (ATcT), the provenance of that value is re-examined in light of new high-end calculations of the Feller-Peterson-Dixon (FPD) variety. An overly optimistic determination of the vaporization enthalpy of hydrazine, which created an unrealistically strong connection between the gas phase thermochemistry and the calorimetric results defining the thermochemistry of liquid hydrazine, was identified as the probable culprit. The new enthalpy of formation of gas-phase hydrazine, based on balancing all available knowledge, was determined to be 111.57 ± 0.47 kJ/mol at 0 K (97.42 ± 0.47 kJ/mol at 298.15 K). Close agreement was found between the ATcT (even excluding the latest theoretical result) and the FPD enthalpy.

  16. Enthalpy of mixing of liquid Co–Sn alloys

    Science.gov (United States)

    Yakymovych, A.; Fürtauer, S.; Elmahfoudi, A.; Ipser, H.; Flandorfer, H.

    2014-01-01

    A literature overview of enthalpy of mixing data for liquid Co–Sn alloys shows large scattering but no clear temperature dependence. Therefore drop calorimetry was performed in the Co–Sn system at twelve different temperatures in 100 K steps in the temperature range (673 to 1773) K. The integral enthalpy of mixing was determined starting from 1173 K and fitted to a standard Redlich–Kister polynomial. In addition, the limiting partial molar enthalpy of Co in Sn was investigated by small additions of Co to liquid Sn at temperatures (673 to 1773) K. The integral and partial molar enthalpies of the Co–Sn system generally show an exothermic mixing behavior. Significant temperature dependence was detected for the enthalpies of mixing. The minimum integral enthalpy values vary with rising temperature from approx. −7820 J/mol at T = 1173 K to −1350 J/mol at T = 1773 K; the position of the minimum is between (59 and 61) at.% Co. The results are discussed and compared with literature data available for this system. X-ray studies and scanning electron microscopy of selected alloys obtained from the calorimetric measurements were carried out in order to check the completeness of the solution process. PMID:24994940

  17. Enthalpy of mixing of liquid Co-Sn alloys.

    Science.gov (United States)

    Yakymovych, A; Fürtauer, S; Elmahfoudi, A; Ipser, H; Flandorfer, H

    2014-07-01

    A literature overview of enthalpy of mixing data for liquid Co-Sn alloys shows large scattering but no clear temperature dependence. Therefore drop calorimetry was performed in the Co-Sn system at twelve different temperatures in 100 K steps in the temperature range (673 to 1773) K. The integral enthalpy of mixing was determined starting from 1173 K and fitted to a standard Redlich-Kister polynomial. In addition, the limiting partial molar enthalpy of Co in Sn was investigated by small additions of Co to liquid Sn at temperatures (673 to 1773) K. The integral and partial molar enthalpies of the Co-Sn system generally show an exothermic mixing behavior. Significant temperature dependence was detected for the enthalpies of mixing. The minimum integral enthalpy values vary with rising temperature from approx. -7820 J/mol at T  = 1173 K to -1350 J/mol at T  = 1773 K; the position of the minimum is between (59 and 61) at.% Co. The results are discussed and compared with literature data available for this system. X-ray studies and scanning electron microscopy of selected alloys obtained from the calorimetric measurements were carried out in order to check the completeness of the solution process.

  18. Enthalpy-entropy compensation: the role of solvation.

    Science.gov (United States)

    Dragan, Anatoliy I; Read, Christopher M; Crane-Robinson, Colyn

    2017-05-01

    Structural modifications to interacting systems frequently lead to changes in both the enthalpy (heat) and entropy of the process that compensate each other, so that the Gibbs free energy is little changed: a major barrier to the development of lead compounds in drug discovery. The conventional explanation for such enthalpy-entropy compensation (EEC) is that tighter contacts lead to a more negative enthalpy but increased molecular constraints, i.e., a compensating conformational entropy reduction. Changes in solvation can also contribute to EEC but this contribution is infrequently discussed. We review long-established and recent cases of EEC and conclude that the large fluctuations in enthalpy and entropy observed are too great to be a result of only conformational changes and must result, to a considerable degree, from variations in the amounts of water immobilized or released on forming complexes. Two systems exhibiting EEC show a correlation between calorimetric entropies and local mobilities, interpreted to mean conformational control of the binding entropy/free energy. However, a substantial contribution from solvation gives the same effect, as a consequence of a structural link between the amount of bound water and the protein flexibility. Only by assuming substantial changes in solvation-an intrinsically compensatory process-can a more complete understanding of EEC be obtained. Faced with such large, and compensating, changes in the enthalpies and entropies of binding, the best approach to engineering elevated affinities must be through the addition of ionic links, as they generate increased entropy without affecting the enthalpy.

  19. [Enthalpy stabilization of chicken egg lysozyme in aqueous dimethylsulfoxide solutions].

    Science.gov (United States)

    Kovrigin, E L; Kirkitadze, M D; Potekhin, S A

    1996-01-01

    Scanning microcalorimetry data have been used to plot the dependences of the denaturation enthalpy of hen egg lysozyme on dimethylsulfoxide concentration at fixed temperatures. It has been shown that at dimethylsulfoxide concentrations below 40% (v/v) the enthalpy does not depend on pH of the medium. An increase of dimethylsulfoxide concentrations in this range leads to a linear growth of enthalpy. The rate of enthalpy growth decreases with the temperature increase. The denaturation enthalpy begins to considerably depend on pH at dimethylsulfoxide concentrations more than 40%. Spectroscopy data indicate that conformational changes occur in the protein in this range of concentrations already at room temperature, whereas according to scanning microcalorimetry, they take place at much higher temperatures. This difference is probably due to a decrease of the real temperature of protein melting below room temperature and a very inhibited character of the denaturational transition. This results in a decrease of calorimetric enthalpy at acidic pH owing to incomplete protein renaturation upon calorimeter cooling to the starting point.

  20. Meridional Motions and Reynolds Stress Determined by Using Kanzelhöhe Drawings and White Light Solar Images from 1964 to 2016

    Science.gov (United States)

    Ruždjak, Domagoj; Sudar, Davor; Brajša, Roman; Skokić, Ivica; Poljančić Beljan, Ivana; Jurdana-Šepić, Rajka; Hanslmeier, Arnold; Veronig, Astrid; Pötzi, Werner

    2018-04-01

    Sunspot position data obtained from Kanzelhöhe Observatory for Solar and Environmental Research (KSO) sunspot drawings and white light images in the period 1964 to 2016 were used to calculate the rotational and meridional velocities of the solar plasma. Velocities were calculated from daily shifts of sunspot groups and an iterative process of calculation of the differential rotation profiles was used to discard outliers. We found a differential rotation profile and meridional motions in agreement with previous studies using sunspots as tracers and conclude that the quality of the KSO data is appropriate for analysis of solar velocity patterns. By analyzing the correlation and covariance of meridional velocities and rotation rate residuals we found that the angular momentum is transported towards the solar equator. The magnitude and latitudinal dependence of the horizontal component of the Reynolds stress tensor calculated is sufficient to maintain the observed solar differential rotation profile. Therefore, our results confirm that the Reynolds stress is the dominant mechanism responsible for transport of angular momentum towards the solar equator.

  1. Meridional Flow Variations in Cycles 23 and 24: Active Latitude Control of Sunspot Cycle Amplitudes

    Science.gov (United States)

    Hathaway, David H.; Upton, Lisa

    2013-01-01

    We have measured the meridional motions of magnetic elements observed in the photosphere over sunspot cycles 23 and 24 using magnetograms from SOHO/MDI and SDO/HMI. Our measurements confirm the finding of Komm, Howard, and Harvey (1993) that the poleward meridional flow weakens at cycle maxima. Our high spatial and temporal resolution analyses show that this variation is in the form of a superimposed inflow toward the active latitudes. This inflow is weaker in cycle 24 when compared to the inflow in 23, the stronger cycle. This systematic modulation of the meridional flow can modulate the amplitude of the following sunspot cycle through its influence on the Sun's polar fields.

  2. Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium

    Science.gov (United States)

    Hunt, J. L.; Boney, L. R.

    1973-01-01

    Equations and in computer code are presented for the thermodynamic and transport properties of gaseous, undissociated tetrafluoromethane (CF4) in chemical equilibrium. The computer code calculates the thermodynamic and transport properties of CF4 when given any two of five thermodynamic variables (entropy, temperature, volume, pressure, and enthalpy). Equilibrium thermodynamic and transport property data are tabulated and pressure-enthalpy diagrams are presented.

  3. A multimodel comparison of centennial Atlantic meridional overturning circulation variability

    Energy Technology Data Exchange (ETDEWEB)

    Menary, Matthew B.; Vellinga, Michael; Palmer, Matthew D. [Met Office Hadley Centre, Exeter, Devon (United Kingdom); Park, Wonsun; Latif, Mojib [IFM-GEOMAR, Leibniz-Institut fuer Meereswissenschaften, Kiel (Germany); Lohmann, Katja; Jungclaus, Johann H. [Max Planck Inst Meteorol, Hamburg (Germany)

    2012-06-15

    A mechanism contributing to centennial variability of the Atlantic Meridional Overturning Circulation (AMOC) is tested with multi-millennial control simulations of several coupled general circulation models (CGCMs). These are a substantially extended integration of the 3rd Hadley Centre Coupled Climate Model (HadCM3), the Kiel Climate Model (KCM), and the Max Plank Institute Earth System Model (MPI-ESM). Significant AMOC variability on time scales of around 100 years is simulated in these models. The centennial mechanism links changes in the strength of the AMOC with oceanic salinities and surface temperatures, and atmospheric phenomena such as the Intertropical Convergence Zone (ITCZ). 2 of the 3 models reproduce all aspects of the mechanism, with the third (MPI-ESM) reproducing most of them. A comparison with a high resolution paleo-proxy for Sea Surface Temperatures (SSTs) north of Iceland over the last 4,000 years, also linked to the ITCZ, suggests that elements of this mechanism may also be detectable in the real world. (orig.)

  4. Late Holocene sea level variability and Atlantic Meridional Overturning Circulation

    Science.gov (United States)

    Cronin, Thomas M.; Farmer, Jesse R.; Marzen, R. E.; Thomas, E.; Varekamp, J.C.

    2014-01-01

    Pre-twentieth century sea level (SL) variability remains poorly understood due to limits of tide gauge records, low temporal resolution of tidal marsh records, and regional anomalies caused by dynamic ocean processes, notably multidecadal changes in Atlantic Meridional Overturning Circulation (AMOC). We examined SL and AMOC variability along the eastern United States over the last 2000 years, using a SL curve constructed from proxy sea surface temperature (SST) records from Chesapeake Bay, and twentieth century SL-sea surface temperature (SST) relations derived from tide gauges and instrumental SST. The SL curve shows multidecadal-scale variability (20–30 years) during the Medieval Climate Anomaly (MCA) and Little Ice Age (LIA), as well as the twentieth century. During these SL oscillations, short-term rates ranged from 2 to 4 mm yr−1, roughly similar to those of the last few decades. These oscillations likely represent internal modes of climate variability related to AMOC variability and originating at high latitudes, although the exact mechanisms remain unclear. Results imply that dynamic ocean changes, in addition to thermosteric, glacio-eustatic, or glacio-isostatic processes are an inherent part of SL variability in coastal regions, even during millennial-scale climate oscillations such as the MCA and LIA and should be factored into efforts that use tide gauges and tidal marsh sediments to understand global sea level rise.

  5. Upgrading the Arecibo Potassium Lidar Receiver for Meridional Wind Measurements

    Science.gov (United States)

    Piccone, A. N.; Lautenbach, J.

    2017-12-01

    Lidar can be used to measure a plethora of variables: temperature, density of metals, and wind. This REU project is focused on the set up of a semi steerable telescope that will allow the measurement of meridional wind in the mesosphere (80-105 km) with Arecibo Observatory's potassium resonance lidar. This includes the basic design concept of a steering system that is able to turn the telescope to a maximum of 40°, alignment of the mirror with the telescope frame to find the correct focusing, and the triggering and programming of a CCD camera. The CCD camera's purpose is twofold: looking though the telescope and matching the stars in the field of view with a star map to accurately calibrate the steering system and determining the laser beam properties and position. Using LabVIEW, the frames from the CCD camera can be analyzed to identify the most intense pixel in the image (and therefore the brightest point in the laser beam or stars) by plotting average pixel values per row and column and locating the peaks of these plots. The location of this pixel can then be plotted, determining the jitter in the laser and position within the field of view of the telescope.

  6. Meridional equatorial electrojet current in the American sector

    Directory of Open Access Journals (Sweden)

    R. G. Rastogi

    Full Text Available Huancayo is the only equatorial electrojet station where the daytime increase of horizontal geomagnetic field (H is associated with a simultaneous increase of eastward geomagnetic field (Y. It is shown that during the counter electrojet period when ∆H is negative, ∆Y also becomes negative. Thus, the diurnal variation of ∆Y at equatorial latitudes is suggested to be a constituent part of the equatorial electrojet current system. Solar flares are known to increase the H field at an equatorial station during normal electrojet conditions (nej. At Huancayo, situated north of the magnetic equator, the solar flare effect, during nej, consists of positive impulses in H and Y and negative impulse in Z field. During counter electrojet periods (cej, a solar flare produces a negative impulse in H and Y and a positive impulse in Z at Huancayo. It is concluded that both the zonal and meridional components of the equatorial electrojet in American longitudes, as in Indian longitudes, flows in the same, E region of the ionosphere.

    Key words. Geomagnetism and paleomagnetism (dynamo theories · Ionosphere (equatorial ionosphere; ionosphere disturbances

  7. Meridional equatorial electrojet current in the American sector

    Directory of Open Access Journals (Sweden)

    R. G. Rastogi

    1999-02-01

    Full Text Available Huancayo is the only equatorial electrojet station where the daytime increase of horizontal geomagnetic field (H is associated with a simultaneous increase of eastward geomagnetic field (Y. It is shown that during the counter electrojet period when ∆H is negative, ∆Y also becomes negative. Thus, the diurnal variation of ∆Y at equatorial latitudes is suggested to be a constituent part of the equatorial electrojet current system. Solar flares are known to increase the H field at an equatorial station during normal electrojet conditions (nej. At Huancayo, situated north of the magnetic equator, the solar flare effect, during nej, consists of positive impulses in H and Y and negative impulse in Z field. During counter electrojet periods (cej, a solar flare produces a negative impulse in H and Y and a positive impulse in Z at Huancayo. It is concluded that both the zonal and meridional components of the equatorial electrojet in American longitudes, as in Indian longitudes, flows in the same, E region of the ionosphere.Key words. Geomagnetism and paleomagnetism (dynamo theories · Ionosphere (equatorial ionosphere; ionosphere disturbances

  8. A commentary on the Atlantic meridional overturning circulation stability in climate models

    Science.gov (United States)

    Gent, Peter R.

    2018-02-01

    The stability of the Atlantic meridional overturning circulation (AMOC) in ocean models depends quite strongly on the model formulation, especially the vertical mixing, and whether it is coupled to an atmosphere model. A hysteresis loop in AMOC strength with respect to freshwater forcing has been found in several intermediate complexity climate models and in one fully coupled climate model that has very coarse resolution. Over 40% of modern climate models are in a bistable AMOC state according to the very frequently used simple stability criterion which is based solely on the sign of the AMOC freshwater transport across 33° S. In a recent freshwater hosing experiment in a climate model with an eddy-permitting ocean component, the change in the gyre freshwater transport across 33° S is larger than the AMOC freshwater transport change. This casts very strong doubt on the usefulness of this simple AMOC stability criterion. If a climate model uses large surface flux adjustments, then these adjustments can interfere with the atmosphere-ocean feedbacks, and strongly change the AMOC stability properties. AMOC can be shut off for many hundreds of years in modern fully coupled climate models if the hosing or carbon dioxide forcing is strong enough. However, in one climate model the AMOC recovers after between 1000 and 1400 years. Recent 1% increasing carbon dioxide runs and RCP8.5 future scenario runs have shown that the AMOC reduction is smaller using an eddy-resolving ocean component than in the comparable standard 1° ocean climate models.

  9. Wind Diffusivity Current, METOP ASCAT, 0.25 degrees, Global, Near Real Time, Meridional

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NOAA CoastWatch distributes near real time Ekman current (in zonal, meridional, and modulus sets) and Ekman upwelling data. This data begins with wind velocity...

  10. Wind Stress, METOP ASCAT, 0.25 degrees, Global, Near Real Time, Meridional

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NOAA CoastWatch distributes near real time wind stress data in zonal, meridional, modulus, and wind stress curl sets. This data begins with wind velocity...

  11. A Numerical Study on the Impeller Meridional Curvature of High Pressure Multistage Pump

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Deok Su; Jean, Sang Gyu; Mamatov, Sanjar [Hyosung Goodsprings, Inc., Busan (Korea, Republic of); Park, Warn Gyu [Pusan Nat’l Univ., Busan (Korea, Republic of)

    2017-07-15

    This paper presents the hydraulic design an impeller and radial diffuser of a high-pressure multistage pump for reverse osmosis. The flow distribution and hydraulic performance for the meridional design of the impeller were analyzed numerically. Optimization was conducted based on the response surface method by varying the hub and shroud meridional curvatures, while maintaining the impeller outlet diameter, outlet width, and eye diameter constant. The analysis results of the head and efficiency with the variation in the impeller meridional profile showed that angle of the front shroud near the impeller outlet (εDs) had the highest effect on head increase, while the hub inlet length (d1i) and shroud curvature (Rds) had the highest effect on efficiency. From the meridional profile variation, an approximately 0.5% increase in efficiency was observed compared with the base model (case 25).

  12. Wind Stress, QuikSCAT SeaWinds, 0.25 degrees, Global, Science Quality, Meridional

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NOAA CoastWatch distributes science quality wind stress data in zonal, meridional, modulus, and wind stress curl sets. This data begins with wind velocity...

  13. Currents, HF Radio-derived, SF Bay Outlet, Normal Model, Meridional, EXPERIMENTAL

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The data is the meridional component of ocean surface currents derived from High Frequency Radio-derived measurements, with missing values filled in by a normal...

  14. Currents, HF Radio-derived, SF Bay Outlet, 1 hr, Meridional, EXPERIMENTAL

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The data is the 1 hour average of the meridional component of ocean surface currents derived from High Frequency Radio-derived measurements. THIS IS AN EXPERIMENTAL...

  15. Currents, HF Radio-derived, Monterey Bay, 25 hr, Meridional, EXPERIMENTAL

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The data is the 25 hour running average of the meridional component of ocean surface currents derived from High Frequency Radio-derived measurements. THIS IS AN...

  16. Currents, HF Radio-derived, Ano Nuevo, 25 hr, Meridional, EXPERIMENTAL

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The data is the 25 hour running average of the meridional component of ocean surface currents derived from High Frequency Radio-derived measurements. THIS IS AN...

  17. Currents, HF Radio-derived, Ano Nuevo, 1 hr, Meridional, EXPERIMENTAL

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The data is the 1 hour average of the meridional component of ocean surface currents derived from High Frequency Radio-derived measurements. THIS IS AN EXPERIMENTAL...

  18. Currents, HF Radio-derived, Monterey Bay, 1 hr, Meridional, EXPERIMENTAL

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The data is the 1 hour average of the meridional component of ocean surface currents derived from High Frequency Radio-derived measurements. THIS IS AN EXPERIMENTAL...

  19. Currents, HF Radio-derived, Bodega Bay, 1 hr, Meridional, EXPERIMENTAL

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The data is the 1 hour average of the meridional component of ocean surface currents derived from High Frequency Radio-derived measurements. THIS IS AN EXPERIMENTAL...

  20. Currents, HF Radio-derived, SF Bay, 33 hr, Meridional, EXPERIMENTAL

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The data is the 33 hour running average of the meridional component of ocean surface currents derived from High Frequency Radio-derived measurements. THIS IS AN...

  1. Currents, HF Radio-derived, SF Bay, 25 hr, Meridional, EXPERIMENTAL

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The data is the 25 hour running average of the meridional component of ocean surface currents derived from High Frequency Radio-derived measurements. THIS IS AN...

  2. Enthalpy Differences of the n-Pentane Conformers.

    Science.gov (United States)

    Csontos, József; Nagy, Balázs; Gyevi-Nagy, László; Kállay, Mihály; Tasi, Gyula

    2016-06-14

    The energy and enthalpy differences of alkane conformers in various temperature ranges have been the subject for both experimental and theoretical studies over the last few decades. It was shown previously for the conformers of butane [G. Tasi et al., J. Chem. Theory Comput. 2012, 8, 479-486] that quantum chemical results can compete with spectroscopic techniques and results obtained even from the most carefully performed experiments could be biased due to the improper statistical model utilized to evaluate the raw experimental data. In the current study, on one hand, the experimental values and their uncertainties for the enthalpy differences for pentane conformers are re-evaluated using the appropriate statistical model. On the other hand, a coupled-cluster-based focal-point analysis has been performed to calculate energy and enthalpy differences for the conformers of pentane. The model chemistry defined in this study includes contributions up to the perturbative quadruple excitations augmented with further small correction terms beyond the Born-Oppenheimer and nonrelativistic approximations. Benchmark quality energy and enthalpy differences for the pentane conformers are given at temperatures 0 and 298.15 K as well as for the various temperature ranges used in the gas-phase experimental measurements. Furthermore, a slight positive shift for the experimental enthalpy differences is also predicted due to an additional Raman active band belonging to the gauche-gauche conformer.

  3. Enthalpy of Formation and O-H Bond Dissociation Enthalpy of Phenol: Inconsistency between Theory and Experiment.

    Science.gov (United States)

    Dorofeeva, Olga V; Ryzhova, Oxana N

    2016-04-21

    Gas-phase O–H homolytic bond dissociation enthalpy in phenol, DH298°(C6H5O–H), is still disputed, despite a large number of experimental and computational studies. In estimating this value, the experimental enthalpy of formation of phenol, ΔfH298°(C6H5OH, g) = −96.4 ± 0.6 kJ/mol (Cox, J. D. Pure Appl. Chem. 1961, 2, 125−128), is often used assuming high accuracy of the experimental value. In the present work a substantially less negative value of ΔfH298°(C6H5OH, g) = −91.8 ± 2.5 kJ/mol was calculated combining G4 theory with an isodesmic reaction approach. A benchmark quality of this result was achieved by using a large number of reliable reference species in isodesmic reaction calculations. Among these are the most accurate ΔfH298° values currently available from the Active Thermochemical Tables (ATcT) for 36 species (neutral molecules, radicals, and ions), anisole with recently reassessed enthalpy of formation, and 13 substituted phenols. The internal consistency of the calculated ΔfH298°(C6H5OH, g) value with the experimental enthalpies of formation of more than 50 reference species suggests that the reported experimental enthalpy of formation of phenol is in error. Taking into account that the enthalpy of formation of phenol has not been investigated experimentally since 1961, the new measurements would be extremely valuable. Using the accurate enthalpies of formation of C6H5OH and C6H5O• calculated in the present work, we obtained DH298°(C6H5O–H) = 369.6 ± 4.0 kJ/mol. This value is in satisfactory agreement with that determined from the most precise experimental measurement.

  4. The excess enthalpies of liquid Ge-Pb-Te alloys

    International Nuclear Information System (INIS)

    Blachnik, R.; Binder, J.; Schlieper, A.

    1997-01-01

    The excess enthalpies of liquid alloys in the ternary system Ge-Pb-Te were determined at 1210 K in a heat flow calorimeter for five sections Ge y Pb 1-y -Te with y = 0.2, 0.4, 0.5, 0.6 and 0.8 and at 1153 K for Ge 0.5 Pb 0.5 -Te. The enthalpy surface in the ternary system is determined by a valley of exothermic minima, stretching from an exothermic minimum at the composition GeTe to one at the composition PbTe in the respective binaries. The excess enthalpies in the limiting metallic binary were adapted with the Redlich-Kister formalism. For the description of the thermodynamic functions in the ternary system the equation of Bonnier was taken using ternary coefficients. The calculated curves are in good agreement with the experimental data. (orig.)

  5. Status on high enthalpy geothermal resources in Greece

    International Nuclear Information System (INIS)

    Koutinas, G.A.

    1990-01-01

    Greece is privileged to have many high and medium enthalpy geothermal resources. Related activities during the last 5 years were conducted mainly on the previously discovered geothermal fields of Milos, Nisyros and Lesvos islands, without any deep geothermal drilling. Most efforts were focused on the demonstration of a high enthalpy geothermal reservoir on Milos, by generating electricity from high salinity fluid, with a 2 MW pilot plant. Significant experience has been gained there, by solving technical problems, but still site specific constraints have to be overcome in order to arrive at a comprehensive feasibility study, leading to the development phase. A pre-feasibility study has been carried out in the Nisyros geothermal field. Moreover, a detailed geoscientific exploration program has been completed on Lesvos island, where very promising geothermal areas have been identified. In this paper, reference is made to the most important data concerning high enthalpy geothermal resources by emphasizing the Milos geothermal field

  6. Atlantic Meridional Overturning Circulation response to idealized external forcing

    Energy Technology Data Exchange (ETDEWEB)

    Park, W.; Latif, M. [Leibniz-Institut fuer Meereswissenschaften an der Universitaet Kiel, Kiel (Germany)

    2012-10-15

    The response of the Atlantic Meridional Overturning Circulation (AMOC) to idealized external (solar) forcing is studied in terms of the internal (unforced) AMOC modes with the Kiel Climate Model (KCM), a coupled atmosphere-ocean-sea ice general circulation model. The statistical investigation of KCM's internal AMOC variability obtained from a multi-millennial control run yields three distinct modes: a multi-decadal mode with a period of about 60 years, a quasi-centennial mode with a period of about 100 years and a multi-centennial mode with a period of about 300-400 years. Most variance is explained by the multi-centennial mode, and the least by the quasi-centennial mode. The solar constant varies sinusoidally with two different periods (100 and 60 years) in forced runs with KCM. The AMOC response to the external forcing is rather complex and nonlinear. It involves strong changes in the frequency structure of the variability. While the control run depicts multi-timescale behavior, the AMOC variability in the experiment with 100 year forcing period is channeled into a relatively narrow band centered near the forcing period. It is the quasi-centennial AMOC mode with a period of just under 100 years which is excited, although it is heavily damped in the control run. Thus, the quasi-centennial mode retains its period which does not correspond exactly to the forcing period. Surprisingly, the quasi-centennial mode is also most strongly excited when the forcing period is set to 60 years, the period of the multi-decadal mode which is rather prominent in the control run. It is largely the spatial structure of the forcing rather than its period that determines which of the three internal AMOC modes is excited. The results suggest that we need to understand the full modal structure of the internal AMOC variability in order to understand the circulation's response to external forcing. This could be a challenge for climate models: we cannot necessarily expect that the

  7. Contrasting meridional structures of stratospheric and tropospheric planetary wave variability in the Northern Hemisphere

    Directory of Open Access Journals (Sweden)

    Cheng Sun

    2014-11-01

    Full Text Available The meridional structures of stratospheric and tropospheric planetary wave variability (PWV over the Northern Hemisphere (NH extratropics were investigated and compared using reanalysis data. By performing the spherical double Fourier series expansion of geopotential height data, the horizontal structures of PWV at each vertical level could be examined in the two-dimensional (2D wavenumber (zonal and meridional wavenumbers space. Comparing the amplitudes of wave components during the last three decades, the results suggested that the structures of PWV in the NH troposphere significantly differ from the stratospheric counterparts. The PWV in the troposphere shows multiple meridional wave-like structures, most pronounced for the meridional dipole; while in contrast, PWV in the stratosphere mainly shows large-scale zonal wave patterns, dominated by zonal waves 1 and 2, and have little wave-like fluctuation in the latitudinal direction. The dominant patterns of the NH PWV also show contrasting features of meridional structure between the stratosphere and the troposphere. As represented in the 2D wavenumber space, the leading two empirical orthogonal functions of PWV in the stratosphere largely exhibit the zonal wave 1 pattern, while those in the troposphere clearly show meridional wave-like structures and are dominated by the dipole. The refractive index was derived based on the zonal mean basic state to qualitatively interpret the observational findings. The results suggested that the basic state in the NH troposphere is much more favourable for latitudinally propagating stationary waves than the stratosphere. The difference in meridional structure between stratospheric and tropospheric planetary waves can be well captured in a linear baroclinic model with the observed zonal mean basic state. Furthermore, both theoretical and modelling analyses demonstrated that the fact that zonal wave patterns are preferred in the NH stratosphere may be partly

  8. Enthalpy and void distributions in subchannels of PHWR fuel bundles

    Energy Technology Data Exchange (ETDEWEB)

    Park, J. W.; Choi, H.; Rhee, B. W. [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    1998-12-31

    Two different types of the CANDU fuel bundles have been modeled for the ASSERT-IV code subchannel analysis. From calculated values of mixture enthalpy and void fraction distribution in the fuel bundles, it is found that net buoyancy effect is pronounced in the central region of the DUPIC fuel bundle when compared with the standard CANDU fuel bundle. It is also found that the central region of the DUPIC fuel bundle can be cooled more efficiently than that of the standard fuel bundle. From the calculated mixture enthalpy distribution at the exit of the fuel channel, it is found that the mixture enthalpy and void fraction can be highest in the peripheral region of the DUPIC fuel bundle. On the other hand, the enthalpy and the void fraction were found to be highest in the central region of the standard CANDU fuel bundle at the exit of the fuel channel. This study shows that the subchannel analysis is very useful in assessing thermal behavior of the fuel bundle that could be used in CANDU reactors. 10 refs., 4 figs., 2 tabs. (Author)

  9. Bond dissociation enthalpies of a pinoresinol lignin model compound

    Science.gov (United States)

    Thomas Elder

    2014-01-01

    ABSTRACT: The pinoresinol unit is one of the principal interunit linkages in lignin. As such, its chemistry and properties are of major importance in understanding the behavior or the polymer. This work examines the homolytic cleavage of the pinoresinol system, representing the initial step in thermal degradation. The bond dissociation enthalpy of this reaction has...

  10. Calculation of enthalpies of formation of actinide nitrides

    Czech Academy of Sciences Publication Activity Database

    Sedmidubský, D.; Konings, R.J.M.; Novák, Pavel

    2005-01-01

    Roč. 344, - (2005), s. 40-44 ISSN 0022-3115 Institutional research plan: CEZ:AV0Z1010914 Keywords : enthalpy * actinide nitrides * ab-initio theory Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.414, year: 2005

  11. THE THERMAL CHARACTERIZATION OF MULTICOMPONENT SYSTEMS BY ENTHALPY RELAXATION

    NARCIS (Netherlands)

    TENBRINKE, G; OUDHUIS, L; ELLIS, TS

    1994-01-01

    The phenomenon of enthalpy relaxation of amorphous glassy polymers has been developed into an analytical tool which can be applied to elucidate phase behavior and morphologically related phenomena of multi-component systems. We have both reviewed the experimental details concerning its application,

  12. Protein Transfer Free Energy Obeys Entropy-Enthalpy Compensation.

    Science.gov (United States)

    Mills, Eric A; Plotkin, Steven S

    2015-11-05

    We have found significant entropy-enthalpy compensation for the transfer of a diverse set of two-state folding proteins from water into water containing a diverse set of cosolutes, including osmolytes, denaturants, and crowders. In extracting thermodynamic parameters from experimental data, we show the potential importance of accounting for the cosolute concentration-dependence of the heat capacity change upon unfolding, as well as the potential importance of the temperature-dependence of the heat capacity change upon unfolding. We introduce a new Monte Carlo method to estimate the experimental uncertainty in the thermodynamic data and use this to show by bootstrapping methods that entropy-enthalpy compensation is statistically significant, in spite of large, correlated scatter in the data. We show that plotting the data at the transition midpoint provides the most accurate experimental values by avoiding extrapolation errors due to uncertainty in the heat capacity, and that this representation exhibits the strongest evidence of compensation. Entropy-enthalpy compensation is still significant at lab temperature however. We also find that compensation is still significant when considering variations due to heat capacity models, as well as typical measurement discrepancies lab-to-lab when such data is available. Extracting transfer entropy and enthalpy along with their uncertainties can provide a valuable consistency check between experimental data and simulation models, which may involve tests of simulated unfolded ensembles and/or models of the transfer free energy; we include specific applications to cold shock protein and protein L.

  13. Enthalpy of Vaporization and Vapor Pressures: An Inexpensive Apparatus

    Science.gov (United States)

    Battino, Rubin; Dolson, David A.; Hall, Michael A.; Letcher, Trevor M.

    2007-01-01

    A simple and inexpensive method to determine the enthalpy of vaporization of liquids by measuring vapor pressure as a function of temperature is described. The vapor pressures measured with the stopcock cell were higher than the literature values and those measured with the sidearm rubber septum cell were both higher and lower than literature…

  14. Enthalpy - entropy compensation effect in grain boundary phenomena

    Czech Academy of Sciences Publication Activity Database

    Lejček, Pavel

    2005-01-01

    Roč. 96, č. 10 (2005), s. 1129-1133 ISSN 0044-3093 R&D Projects: GA MPO(CZ) FF-P2/053 Institutional research plan: CEZ:AV0Z10100520 Keywords : compensation effect * enthalpy * entropy * thermodynamics * grain boundary Subject RIV: BJ - Thermodynamics Impact factor: 0.842, year: 2005

  15. Enthalpy and heat capacity of the actinide oxides

    International Nuclear Information System (INIS)

    Fink, J.K.

    1982-01-01

    The available enthalpy data on UO 2 , ThO 2 , PuO 2 , (Th, U)O 2 , and (Pu, U)O 2 have been analyzed and equations have been derived to fit the data. Phase transitions were found in UO 2 , ThO 2 (Th, U)O 2 , and (Pu, U)O 2 . The high temperature PuO 2 data were too scattered to determine whether a phase transition exists. Above the phase transition temperature, the enthalpy data were fit with a linear equation. Enthalpy data for PuO 2 and ThO 2 below the phase transition temperature were fit with two-term equations whose contributions are due to phonons and thermal expansion. For UO 2 below its phase transition, a term for an electronic contribution was added to this basic equation. Below the phase transitions for (Th, U)O 2 , enthalpy data were fit by a mole average of the equations used to fit the ThO 2 and UO 2 data below their phase transitions; however, the mole average equation was not valid for 90 and 92% ThO 2 in the mixed oxide. Since it was found that mole averages of the PuO 2 and UO 2 data do not fit the (Pu, U)O 2 data, these data were fit with an equation of the same form as that used for UO 2 . 51 references, 14 figures, 7 tables

  16. Aerosol volatility and enthalpy of sublimation of carboxylic acids.

    Science.gov (United States)

    Salo, Kent; Jonsson, Asa M; Andersson, Patrik U; Hallquist, Mattias

    2010-04-08

    The enthalpy of sublimation has been determined for nine carboxylic acids, two cyclic (pinonic and pinic acid) and seven straight-chain dicarboxylic acids (C(4) to C(10)). The enthalpy of sublimation was determined from volatility measurements of nano aerosol particles using a volatility tandem differential mobility analyzer (VTDMA) set-up. Compared to the previous use of a VTDMA, this novel method gives enthalpy of sublimation determined over an extended temperature range (DeltaT approximately 40 K). The determined enthalpy of sublimation for the straight-chain dicarboxylic acids ranged from 96 to 161 kJ mol(-1), and the calculated vapor pressures at 298 K are in the range of 10(-6)-10(-3) Pa. These values indicate that dicarboxylic acids can take part in gas-to-particle partitioning at ambient conditions and may contribute to atmospheric nucleation, even though homogeneous nucleation is unlikely. To obtain consistent results, some experimental complications in producing nanosized crystalline aerosol particles were addressed. It was demonstrated that pinonic acid "used as received" needed a further purification step before being suspended as a nanoparticle aerosol. Furthermore, it was noted from distinct differences in thermal properties that aerosols generated from pimelic acid solutions gave two types of particles. These two types were attributed to crystalline and amorphous configurations, and based on measured thermal properties, the enthalpy of vaporization was 127 kJ mol(-1) and that of sublimation was 161 kJ mol(-1). This paper describes a new method that is complementary to other similar methods and provides an extension of existing experimental data on physical properties of atmospherically relevant compounds.

  17. Geothermal Exploration in Oman: Potential of low-enthalpy Reservoirs for Cooling Purposes

    Science.gov (United States)

    Winterleitner, G.; Schütz, F.; Huenges, E.

    2016-12-01

    Thermally driven cooling is a strong option for the energy system in the sun-belt on Earth, for example on the Arabian Peninsula. The energy for a sustainable cold supply can be developed from geothermal sources. An efficient absorption chiller nominally requires water of at least 90°C. The potential of low-enthalpy geothermal reservoirs in Oman is analyzed in the framework of the interdisciplinary "GeoSolCool" project. The identification of a geothermal reservoir requires knowledge about the temperature distribution with depth and the hydraulic properties of the subsurface, notably permeability and the associated transmissibility. So far very little is known about the lateral and vertical temperature distribution in Oman particularly for the study area which is located near Muscat and part of a Cenozoic foreland basin. Rolandone et al. (2013) determined moderate temperature gradients ranging between 16-42 mKm-1 in south and north Oman. New continuous temperature measurements in several wells, scattered over the study area, will give a more detailed understanding of the temperature pattern, depth of the geothermal target and heat transport processes. An advective component, in an otherwise conduction dominated geothermal play system, is likely due to topography and density driven flow. The occurrence of hot springs along a fault structure separating sedimentary rocks of the foreland basin from an ophiolite complex indicates this and constitutes a potential target for low-enthalpy exploitation. Outcrop samples of the sedimentary succession were taken for petrophysical characterization. These first results highlight the potential of low-enthalpy geothermal reservoirs in the area, which has the potential to contribute to a renewable energy mix in Oman and subsequently on the Arabian Peninsula. Rolandone, F., Lucazeau, F., Leroy, S., Mareschal, J.-C., Jorand, R., Goutorbe, B., and H. Bouquerel 2013, New heat flow measurements in Oman and the thermal state of the

  18. The role of Meridional Overturning Circulation (MOC) on Ancient Climates and Implications for Anthropogenic Climate Change

    Science.gov (United States)

    Cumming, M.

    2017-12-01

    Our increasingly robust history of ancient climates indicates that high latitude glaciation is the ultimate product of an episodic cooling trend that began about 100-million years ago rather than a result of a yet-to-be identified modal change. Antarctic geography (continent surrounded by ocean) allowed ice to develop prior to significant glaciation in the Northern Hemisphere (ocean surrounded by land), but global ice volume generally increased as Earth cooled. The question of what caused the Ice Ages should be reframed as to "What caused the Cenozoic Cooling?" Records tell us that changes in temperature and CO2 levels rise and fall together, however it is not clear when CO2 acts as a driver versus when it is primarily an indicator of temperature change. The episodic nature of the cooling trend suggests other more dynamic phenomena are involved. It is proposed that oceanic meridional overturning circulation (MOC) plays a significant role in regulating Earth's surface temperature. Robust MOC has a cooling effect which results from its sequestration of cold waters (together with their increased heat-absorbing potential) below the surface. Unable to better absorb equatorial insolation for great lengths of time, oceanic deep waters are not able to fully compensate for the heat lost by warm-water transport to Polar Regions. A lag-time between cooling and subsequent warming yields lower operating temperatures commensurate with the strength of global MOC. The long-term decline in global temperatures is largely explained by the tectonic reshaping of ocean basins and the connections between them such that MOC has generally, but not uniformly, increased. Geophysically Influenced MOC (GIMOC) has caused a significant proportion of the lowering of global temperatures in the Cenozoic Era. Short-term disruptions in MOC (and subsequent impacts on global temperatures) were likely involved in Late Pleistocene glacial termination events and may already be compounding present

  19. Variability of the Atlantic meridional overturning circulation in the last millennium and two IPCC scenarios

    Energy Technology Data Exchange (ETDEWEB)

    Ortega, Pablo; Montoya, Marisa; Gonzalez-Rouco, Fidel [Universidad Complutense de Madrid, Ciudad Universitaria, Dpto. Astrofisica y Ciencias de la Atmosfera/Instituto de Geociencias, Facultad de Ciencias Fisicas, Madrid (Spain); Universidad Complutense de Madrid, Ciudad Universitaria, Instituto de Geociencias (UCM-CSIC), Facultad de Ciencias Fisicas, Madrid (Spain); Mignot, Juliette [IPSL/LOCEAN, UPMC/CNRS/IRD/MNHN, Universite Pierre et Marie Curie, Paris Cedex 05 (France); Legutke, Stephanie [Deutsches Klimarechenzentrum (DKRZ), Hamburg (Germany)

    2012-05-15

    The variability of the Atlantic meridional overturning circulation (AMOC) is investigated in several climate simulations with the ECHO-G atmosphere-ocean general circulation model, including two forced integrations of the last millennium, one millennial-long control run, and two future scenario simulations of the twenty-first century. This constitutes a new framework in which the AMOC response to future climate change conditions is addressed in the context of both its past evolution and its natural variability. The main mechanisms responsible for the AMOC variability at interannual and multidecadal time scales are described. At high frequencies, the AMOC is directly responding to local changes in the Ekman transport, associated with three modes of climate variability: El Nino-Southern Oscillation (ENSO), the North Atlantic Oscillation (NAO), and the East Atlantic (EA) pattern. At low frequencies, the AMOC is largely controlled by convection activity south of Greenland. Again, the atmosphere is found to play a leading role in these variations. Positive anomalies of convection are preceded in 1 year by intensified zonal winds, associated in the forced runs to a positive NAO-like pattern. Finally, the sensitivity of the AMOC to three different forcing factors is investigated. The major impact is associated with increasing greenhouse gases, given their strong and persistent radiative forcing. Starting in the Industrial Era and continuing in the future scenarios, the AMOC experiences a final decrease of up to 40% with respect to the preindustrial average. Also, a weak but significant AMOC strengthening is found in response to the major volcanic eruptions, which produce colder and saltier surface conditions over the main convection regions. In contrast, no meaningful impact of the solar forcing on the AMOC is observed. Indeed, solar irradiance only affects convection in the Nordic Seas, with a marginal contribution to the AMOC variability in the ECHO-G runs. (orig.)

  20. Enthalpy of formation of anisole: implications for the controversy on the O-H bond dissociation enthalpy in phenol.

    Science.gov (United States)

    Simões, Ricardo G; Agapito, Filipe; Diogo, Hermínio P; da Piedade, Manuel E Minas

    2014-11-20

    Significant discrepancies in the literature data for the enthalpy of formation of gaseous anisole, ΔfHmo(PhOCH3, g), have fueled an ongoing controversy regarding the most reliable enthalpy of formation of the phenoxy radical and of the gas phase O-H bond dissociation enthalpy, DHo(PhO-H), in phenol. In the present work ΔfHmo(PhOCH3, g) was reassessed using a combination of calorimetric determinations and high-level (W2-F12) ab initio calculations. Static-bomb combustion calorimetry led to the standard molar enthalpy of formation of liquid anisole at 298.15 K, ΔfHmo(PhOCH3, l) = −(117.1 ± 1.4) kJ·mol(-1). The corresponding enthalpy of vaporization was obtained as, ΔvapHmo(PhOCH3) = 46.41 ± 0.26 kJ·mol(-1), by Calvet-drop microcalorimetry. These results give ΔfHmo(PhOCH3, g) = −(70.7 ± 1.4) kJ·mol(-1), in excellent agreement with ΔfHmo(PhOCH3, g) = −(70.8 ± 3.2) kJ·mol(-1), obtained from the W2-F12 calculations. The ΔfHmo(PhOCH3, g) here recommended leads to ΔfHmo(PhO•, g) = 55.5 ± 2.4 kJ·mol(-)1 and DH°(PhO-H) = 368.1 ± 2.6 kJ·mol(-1).

  1. Surface changes in the North Atlantic meridional overturning circulation during the last millennium

    DEFF Research Database (Denmark)

    Wanamaker, Jr., Alan D.; Butler, Paul G.; Scourse, James D.

    2012-01-01

    the past 1,350 years, to reconstruct changes in surface ocean circulation and climate. The water mass tracer data presented here from the North Icelandic shelf, combined with previously published data from the Arctic and subtropical Atlantic, show that surface Atlantic meridional overturning circulation......Despite numerous investigations, the dynamical origins of the Medieval Climate Anomaly and the Little Ice Age remain uncertain. A major unresolved issue relating to internal climate dynamics is the mode and tempo of Atlantic meridional overturning circulation variability, and the significance...... of decadal-to-centennial scale changes in Atlantic meridional overturning circulation strength in regulating the climate of the last millennium. Here we use the time-constrained high-resolution local radiocarbon reservoir age offset derived from an absolutely dated annually resolved shell chronology spanning...

  2. Surface changes in the North Atlantic meridional overturning circulation during the last millennium

    Science.gov (United States)

    Wanamaker, Alan D.; Butler, Paul G.; Scourse, James D.; Heinemeier, Jan; Eiríksson, Jón; Knudsen, Karen Luise; Richardson, Christopher A.

    2012-01-01

    Despite numerous investigations, the dynamical origins of the Medieval Climate Anomaly and the Little Ice Age remain uncertain. A major unresolved issue relating to internal climate dynamics is the mode and tempo of Atlantic meridional overturning circulation variability, and the significance of decadal-to-centennial scale changes in Atlantic meridional overturning circulation strength in regulating the climate of the last millennium. Here we use the time-constrained high-resolution local radiocarbon reservoir age offset derived from an absolutely dated annually resolved shell chronology spanning the past 1,350 years, to reconstruct changes in surface ocean circulation and climate. The water mass tracer data presented here from the North Icelandic shelf, combined with previously published data from the Arctic and subtropical Atlantic, show that surface Atlantic meridional overturning circulation dynamics likely amplified the relatively warm conditions during the Medieval Climate Anomaly and the relatively cool conditions during the Little Ice Age within the North Atlantic sector. PMID:22692542

  3. Escleroplastia meridional: A propósito de un caso en 1999 Meridional scleroplasty: With regard to a case in 1999

    Directory of Open Access Journals (Sweden)

    Enrique J. Machado Fernández

    2000-06-01

    Full Text Available En este artículo se presenta un caso reciente de rechazo al aloplante utilizado para escleroplastia meridional. Se refieren las características del cuadro clínico presentado y su tratamiento. Además, se expresan consideraciones basadas en datos estadísticos y hallazgos anatomopatológicos que fundamentan la suspensión de la práctica de esta técnica en el Centro de Microcirugía Ocular.In present paper, authors present a recent case of rejection to allograft used to meridional scleroplasty. Festures of clinical picture and its treatment are related. Furthermore, we express statistical data based on considerations and anatomic-pathologic findings supporting suspension of practice of this technique in Center of Microsurgery of Eye.

  4. Inter-comparison of stratospheric mean-meridional circulation and eddy mixing among six reanalysis data sets

    Directory of Open Access Journals (Sweden)

    K. Miyazaki

    2016-05-01

    Full Text Available The stratospheric mean-meridional circulation (MMC and eddy mixing are compared among six meteorological reanalysis data sets: NCEP-NCAR, NCEP-CFSR, ERA-40, ERA-Interim, JRA-25, and JRA-55 for the period 1979–2012. The reanalysis data sets produced using advanced systems (i.e., NCEP-CFSR, ERA-Interim, and JRA-55 generally reveal a weaker MMC in the Northern Hemisphere (NH compared with those produced using older systems (i.e., NCEP/NCAR, ERA-40, and JRA-25. The mean mixing strength differs largely among the data products. In the NH lower stratosphere, the contribution of planetary-scale mixing is larger in the new data sets than in the old data sets, whereas that of small-scale mixing is weaker in the new data sets. Conventional data assimilation techniques introduce analysis increments without maintaining physical balance, which may have caused an overly strong MMC and spurious small-scale eddies in the old data sets. At the NH mid-latitudes, only ERA-Interim reveals a weakening MMC trend in the deep branch of the Brewer–Dobson circulation (BDC. The relative importance of the eddy mixing compared with the mean-meridional transport in the subtropical lower stratosphere shows increasing trends in ERA-Interim and JRA-55; this together with the weakened MMC in the deep branch may imply an increasing age-of-air (AoA in the NH middle stratosphere in ERA-Interim. Overall, discrepancies between the different variables and trends therein as derived from the different reanalyses are still relatively large, suggesting that more investments in these products are needed in order to obtain a consolidated picture of observed changes in the BDC and the mechanisms that drive them.

  5. Improvements in launchings and recipients of PIG in Malha de Gasodutos Nordeste Meridional; Melhorias nos lancamentos e recebedores de PIG da Malha de Gasodutos Nordeste Meridional

    Energy Technology Data Exchange (ETDEWEB)

    Maciel, Jairo A.C.; Lemos, Francisco A.C.; Lima, Artur W.R. de S. [PETROBRAS Transporte S.A. (TRANSPETRO), Rio de Janeiro, RJ (Brazil)

    2012-07-01

    This paper describes the study that resulted in the preparation of a project for improvement of launchers and receivers of PIG in facilities maintained and operated by PETROBRAS S.A. (TRANSPETRO) in the Malha de Gasodutos Nordeste Meridional (Malha NEM). The improvements are part of the component in cleaner production system and reduce the risks of accidents and the costs of hazardous waste management.

  6. Interface Enthalpy-Entropy Competition in Nanoscale Metal Hydrides

    Directory of Open Access Journals (Sweden)

    Nicola Patelli

    2018-01-01

    Full Text Available We analyzed the effect of the interfacial free energy on the thermodynamics of hydrogen sorption in nano-scaled materials. When the enthalpy and entropy terms are the same for all interfaces, as in an isotropic bi-phasic system, one obtains a compensation temperature, which does not depend on the system size nor on the relative phase abundance. The situation is different and more complex in a system with three or more phases, where the interfaces have different enthalpy and entropy. We also consider the possible effect of elastic strains on the stability of the hydride phase and on hysteresis. We compare a simple model with experimental data obtained on two different systems: (1 bi-phasic nanocomposites where ultrafine TiH2 crystallite are dispersed within a Mg nanoparticle and (2 Mg nanodots encapsulated by different phases.

  7. Enthalpy-Entropy Compensation upon Molecular Conformational Changes.

    Science.gov (United States)

    Ahmad, Mazen; Helms, Volkhard; Lengauer, Thomas; Kalinina, Olga V

    2015-04-14

    The change in free energy is the dominant factor in all chemical processes; it usually encompasses enthalpy-entropy compensation (EEC). Here, we use the free energy perturbation formalism to show that EEC is influenced by the molecular conformational changes (CCs) of the entire system comprising the solute and by the already known solvent reorganization. The internal changes of enthalpy and the entropy due to CCs upon modifying the interactions (perturbation) cancel each other exactly. The CCs influence the dissipation of the modified interactions and their contributions to the free energy. Using molecular simulations, we show that, for solvation of six different HIV-1 protease inhibitors, CCs in the solute cause EEC as large as 10-30 kcal/mol. Moreover, the EEC due to CCs in HIV-1 protease is shown to vary significantly upon modifying its bound ligand. These findings have important implications for understanding of EEC phenomena and for interpretation of thermodynamic measurements.

  8. Enthalpy-Entropy Compensation (EEC) Effect: A Revisit.

    Science.gov (United States)

    Pan, Animesh; Biswas, Tapas; Rakshit, Animesh K; Moulik, Satya P

    2015-12-31

    A short account of the developments and perspectives of IKR (iso-kinetic relation) and EEC (enthalpy (H) - entropy (S) compensation) has been presented. The IKR and EEC are known to be extra thermodynamic or empirical correlations though linear H-S correlation can be thermodynamically deduced. Attempt has also been made to explain the phenomena in terms of statistical thermodynamics. In this study, we have briefly revisited the fundamentals of both IKR and EEC from kinetic and thermodynamic grounds. A detailed revisit of the EEC phenomenon on varied kinetic and equilibrium processes has been also presented. Possible correlations among the free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes of different similar and nonsimilar chemical processes under varied conditions have been discussed with possible future projections.

  9. Flow enthalpy effects on scramjet mixing and combustion

    Science.gov (United States)

    Riggins, D. W.; Mcclinton, C. R.; Rogers, R. C.

    1992-01-01

    The present analysis of the 3D characteristics of the mixing processes in a scramjet combustor gives attention to the streamwise, vorticity-driven macromixing, as well as shear-driven small-scale mixing, in both an unconfined Mach 6 airstream and a high-enthalpy (Mach-17) confined, Mach 6 airstream. The results obtained indicate that mixing is substantially lower for the high-enthalpy case. The effect of residence time on jet mixing is discussed in view of the production and decay of the axial vorticity, cross-flow velocities, and mean-flow velocities of these confined flows. The effective distance travelled by a fluid particle in the cross-flow, over the combustor length, is used to explain axial vorticity's contribution to mixing.

  10. Estimating the melting point, entropy of fusion, and enthalpy of ...

    Science.gov (United States)

    The entropies of fusion, enthalies of fusion, and melting points of organic compounds can be estimated through three models developed using the SPARC (SPARC Performs Automated Reasoning in Chemistry) platform. The entropy of fusion is modeled through a combination of interaction terms and physical descriptors. The enthalpy of fusion is modeled as a function of the entropy of fusion, boiling point, and fexibility of the molecule. The melting point model is the enthlapy of fusion divided by the entropy of fusion. These models were developed in part to improve SPARC's vapor pressure and solubility models. These models have been tested on 904 unique compounds. The entropy model has a RMS of 12.5 J mol-1K-1. The enthalpy model has a RMS of 4.87 kJ mol-1. The melting point model has a RMS of 54.4°C. Published in the journal, SAR and QSAR in Environmental Research

  11. Combustion energies and formation enthalpies of 2-SH-benzazoles

    International Nuclear Information System (INIS)

    Mentado, Juan; Flores, Henoc; Amador, Patricia

    2008-01-01

    The experimental determinations of combustion energies and the standard molar enthalpies of formation of 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzoxazole are presented. The combustion energies of compounds were determined by using a rotating-bomb calorimeter. The calorimeter used in the present work has been assembled, calibrated, and tested recently in our laboratory with desired results. As combustion auxiliary material, polyethene was used and its combustion energy was determined by using a static-bomb calorimeter. The combustion energies of 2-SH-benzazoles were used to derive the correspondent formation enthalpies in condensate phase at T = 298.15 K. The values of Δ f H m 0 for the compounds are (48.6 ± 1.4) kJ . mol -1 , (85.3 ± 1.5) kJ . mol -1 , and (-112.7 ± 1.4) kJ . mol -1 , respectively

  12. Standard molar enthalpies of formation of sodium alkoxides

    International Nuclear Information System (INIS)

    Chandran, K.; Srinivasan, T.G.; Gopalan, A.; Ganesan, V.

    2007-01-01

    The molar enthalpies of solution of sodium in methanol, ethanol, and n-propanol and of sodium alkoxides in their corresponding alcohols were measured at T=298.15K using an isoperibol solution calorimeter. From these results and other auxiliary data, the standard molar enthalpies of formation, Δ f H m o (RONa,cr) of sodium methoxide, sodium ethoxide, and sodium n-propoxide were calculated and found to be {(-366.21+/-1.38) (-413.39+/-1.45), and (-441.57+/-1.18)}kJ.mol -1 , respectively. A linear correlation has been found between Δ f H m o (RONa)andΔ f H m o (ROH) for R=n-alkyl, enabling the prediction of data for other sodium alkoxides

  13. Determination of the vacancy formation enthalpy for high purity Ni

    International Nuclear Information System (INIS)

    Lynn, K.G.; Snead, C.L. Jr.; Hurst, J.J.; Farrell, K.

    1979-01-01

    Positron-annihilation lifetime measurements have been made on Ni over a temperature range of 4.2 to 1700 K. We find a small change in the lifetime from 4.2 - 900 K indicating a very small thermal-expansion effect. A small precursor effect is observed before the onset of significant vacancy trapping. A monovacancy formation enthalpy of 1.54sub(+0.2)sup(-0.1) eV is extracted without taking divacancies into consideration in the analysis. No detrapping from mono-vacancies is observed even at the higher temperatures. The vacancy formation enthalpy extracted from the lifetime data is compared to values obtained by Doppler-broadening and angular-correlation techniques. (author)

  14. Kinetics and enthalpy of crystallization of uric acid dihydrate

    International Nuclear Information System (INIS)

    Sádovská, Galina; Honcová, Pavla; Sádovský, Zdeněk

    2013-01-01

    Highlights: • The kinetic constant and growth order of crystallization of uric acid dihydrate was calculated. • The equation describing first-order crystal growth was derived. • The enthalpy of crystallization of uric acid dihydrate was determined. - Abstract: The kinetics of crystallization of uric acid dihydrate in aqueous solution with a constant ionic strength 0.3 mol dm −3 NaCl and at thermodynamic and physiological temperature (25 and 37 °C) was studied using isoperibolic reaction twin calorimeter. The enthalpy of crystallization Δ cr H = −47.3 ± 0.9 and −46.2 ± 1.4 kJ mol −1 and kinetic constant k g = 2.0 × 10 −8 and 9.6 × 10 −8 m 4 s −1 mol −1 were determined at 25 and 37 °C, respectively

  15. Determination of the vacancy formation enthalpy for high purity Ni

    International Nuclear Information System (INIS)

    Lynn, K.G.; Snead, C.L. Jr.; Hurst, J.J.; Farrell, K.

    1979-01-01

    Positron-annihilation lifetime measurements have been made on Ni over a temperature range of 4.2 to 1700 K. We find a small change in the lifetime from 4.2 to 900 K indicating a very small thermal-expansion effect. A small precursor effect is observed before the onset of significant vacancy trapping. A monovacancy formation enthalpy of 1.54/sub +0.2//sup -0.1/ eV is extracted without taking divacancies into consideration in the analysis. No detrapping from mono-vacancies is observed even at the higher temperatures. The vacancy formation enthalpy extracted from the lifetime data is compared to values obtained by Doppler-broadening and angular-correlation techniques

  16. The relationship between vapour pressure, vaporization enthalpy, and enthalpy of transfer from solution to gas: An extension of the Martin equation

    International Nuclear Information System (INIS)

    Srisaipet, A.; Aryusuk, K.; Lilitchan, S.; Krisnangkura, K.

    2007-01-01

    Martin's equation, Δ sln g G=Δ sln g G o +zδ sln g G, is extended to cover vaporization free energy (Δ l g G). The extended equation is further expanded in terms of enthalpy and entropy and then used to correlate vaporization enthalpy (Δ l g H) and enthalpy of transfer from solution to gas (Δ sln g H). Data available in the literatures are used to validate and support the speculations derived from the proposed equation

  17. Symmetry-enthalpy correlations in Diels-Alder reactions.

    Science.gov (United States)

    Tuvi-Arad, Inbal; Avnir, David

    2012-08-06

    Woodward-Hoffmann (WH) rules provide strict symmetry selection rules: when they are obeyed, a reaction proceeds; when they are not obeyed, there is no reaction. However, the voluminous experimental literature provides ample evidence that strict compliance to symmetry requirements is not an obstacle for a concerted reaction to proceed, and therefore the idea has developed that it is enough to have a certain degree of the required symmetry to have reactivity. Here we provide quantitative evidence of that link, and show that as one deviates from the desired symmetry, the enthalpy of activation increases, that is, we show that concerted reactions slow down the further they are from the ideal symmetry. Specifically, we study the deviation from mirror symmetry (evaluated with the continuous symmetry measure (CSM)) of the [4+2] carbon skeleton of the transition state of a series of twelve Diels-Alder reactions in seven different solvents (and in the gas phase), in which the dienes are butadiene, cyclopentadiene, cyclohexadiene, and cycloheptadiene; the dienophiles are the 1-, 1,1-, and 1,1,2-cyanoethylene derivatives; the solvents were chosen to sample a range of dielectric constants from heptane to ethanol. These components provide twenty-four symmetry-enthalpy DFT-calculated correlation lines (out of which only one case is a relatively mild exception) that show the general trend of increase in enthalpy as symmetry decreases. The various combinations between the dienophiles, cyanoethylenes, and solvents provide all kinds of sources for symmetry deviations; it is therefore remarkable that although the enthalpy of activation is dictated by various parameters, symmetry emerges as a primary parameter. In our analysis we also bisected this overall picture into solvent effects and geometry variation effects to evaluate under which conditions the electronic effects are more dominant than symmetry effects. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Determination of melting and solidification enthalpy of hypereutectic silumins

    Directory of Open Access Journals (Sweden)

    J. Piątkowski

    2008-04-01

    Full Text Available The study was related with determination of the values of enthalpy of melting and solidification of hypereutectic AlSi18, AlSi21 and AlSi24 silumins modified with phosphorus in the form of Cu-P. The calorimetry, preceded by thermal analysis and derivative thermal analysis (TA and DTA, respectively was carried out on a high-temperature scanning calorimeter, model MHTC-96, made by SETARAM, applying the method of direct determination of parameters of the high-temperature process, and in particular of the enthalpy of phase transformations. Modern control and measuring instruments coupled with PC computer provide a very precise tool for determination of these transformations. An additional advantage was development of appropriate software called „SETSOFT”, owing to which it was possible to determine in an easy way the enthalpy of the investigated phase transformations. Moreover, an additional thermal effect, related most probably with pre-eutectic crystallization of primary silicon, was observed and confirmed by calorimetric examinations.

  19. The Phase Space as a New Representation of the Dynamical Behaviour of Temperature and Enthalpy in a Reefer monitored with a Multidistributed Sensors Network

    OpenAIRE

    Jiménez Ariza, Heidi Tatiana; Correa Hernando, Eva Cristina; Diezma Iglesias, Belen; Silveira, Ana Cecilia; Zócalo, P.; Arranz Saiz, Francisco Javier; Moya Gonzalez, Adolfo; Garrido Izard, Miguel; Barreiro Elorza, Pilar; Ruiz-Altisent, Margarita

    2013-01-01

    The study of temperature gradients in cold stores and containers is a critical issue in the food industry for the quality assurance of products during transport, as well as forminimizing losses. The objective of this work is to develop a new methodology of data analysis based on phase space graphs of temperature and enthalpy, collected by means of multidistributed, low cost and autonomous wireless sensors and loggers. A transoceanic refrigerated transport of lemons in a reefer container ship ...

  20. Transportation

    International Nuclear Information System (INIS)

    Anon.

    1998-01-01

    Here is the decree of the thirtieth of July 1998 relative to road transportation, to trade and brokerage of wastes. It requires to firms which carry out a road transportation as well as to traders and to brokers of wastes to declare their operations to the prefect. The declaration has to be renewed every five years. (O.M.)

  1. Meridional overturning circulation: stability and ocean feedbacks in a box model

    NARCIS (Netherlands)

    Cimatoribus, A.A.; Drijfhout, S.S.; Dijkstra, H.A.|info:eu-repo/dai/nl/073504467

    2014-01-01

    A box model of the inter-hemispheric Atlantic meridional overturning circulation is developed, including a variable pycnocline depth for the tropical and subtropical regions. The circulation is forced by winds over a periodic channel in the south and by freshwater forcing at the surface. The model

  2. Interdecadal North-Atlantic meridional overturning circulation variability in EC-EARTH

    NARCIS (Netherlands)

    Wouters, B.; Drijfhout, D.; Hazeleger, W.

    2012-01-01

    The Atlantic meridional overturning circulation (AMOC) in a 600 years pre-industrial run of the newly developed EC-EARTH model features marked interdecadal variability with a dominant time-scale of 50–60 years. An oscillation of approximately 2 Sverdrup (1 Sv = 106 m3 s-1) is identified, which

  3. Interconverting the matrix and principal-meridional representations of dioptric power and reduced vergence.

    Science.gov (United States)

    Harris, W F

    2000-11-01

    Converting the traditional representation of power as sphere, cylinder and axis to the dioptric power matrix F is usually performed by means of Long's equations and the reverse process by means of Keating's equations. It is sometimes useful to be able to convert directly between the matrix and power expressed in terms of principal powers F1 and F2 along corresponding principal meridians at angles a1 and a2. The equations for interconverting F and the principal-meridional representation expressed as F1(a1)F2 are presented here. Equivalent equations allow direct interconversion of the reduced vergence matrix L and the principal-meridional representation of vergence L1(a1)L2. Vergence becomes infinite at line and point focuses. Similarly effective power and back- and front-vertex power are infinite for some systems. Nevertheless it is possible unambiguously to represent infinite vergence and vertex power in principal-meridional form. However, information is usually lost in these infinite cases when the principal-meridional representation is converted to the matrix representation, and the former is not recoverable from the latter. As a consequence the matrix representation is usually unsatisfactory for vergences and vertex powers that are infinite. On the other hand, the principal-meridional representation of vergence and power is always satisfactory. If one adopts the position that effective powers and vertex powers are really vergences rather than powers then one concludes that the matrix provides a satisfactory representation for powers of thin systems in general but not for vergences. Implied by a vergence at a point is an interval of Sturm. The equations for characterizing the interval from the reduced vergence are presented.

  4. Enthalpy of formation of the cyclohexadienyl radical and the C-H bond enthalpy of 1,4-cyclohexadiene: an experimental and computational re-evaluation.

    Science.gov (United States)

    Gao, Yide; DeYonker, Nathan J; Garrett, E Chauncey; Wilson, Angela K; Cundari, Thomas R; Marshall, Paul

    2009-06-25

    A quantitative understanding of the thermochemistry of cyclohexadienyl radical and 1,4-cyclohexadiene is beneficial for diverse areas of chemistry. Given the interest in these two species, it is surprising that more detailed thermodynamic data concerning the homolytic C-H bond enthalpies of such entities have not been forthcoming. We thus undertook an experimental and computational evaluation of (a) the enthalpy of formation of cyclohexadienyl radical (C(6)H(7)), (b) the homolytic C-H bond enthalpy of 1,4-cyclohexadiene (C(6)H(8)), and (c) the enthalpy of the addition of a hydrogen atom to benzene. Using laser photolysis experiments coupled with highly accurate ab initio quantum mechanical techniques, a newly recommended enthalpy of formation for C(6)H(7) is determined to be 208.0 +/- 3.9 kJ mol(-1), leading to a homolytic bond dissociation enthalpy of 321.7 +/- 2.9 kJ mol(-1), almost 9 kJ mol(-1) higher than previously determined enthalpies that used less certain experimental values for the C(6)H(7) enthalpy of formation.

  5. Transportation

    National Research Council Canada - National Science Library

    Allshouse, Michael; Armstrong, Frederick Henry; Burns, Stephen; Courts, Michael; Denn, Douglas; Fortunato, Paul; Gettings, Daniel; Hansen, David; Hoffman, Douglas; Jones, Robert

    2007-01-01

    .... The ability of the global transportation industry to rapidly move passengers and products from one corner of the globe to another continues to amaze even those wise to the dynamics of such operations...

  6. Speed of Meridional Flows and Magnetic Flux Transport on the Sun

    Czech Academy of Sciences Publication Activity Database

    Švanda, Michal; Kosovichev, A.G.; Zhao, J.

    2007-01-01

    Roč. 607, č. 1 (2007), L69-L72 ISSN 0004-637X Grant - others:EU(XE) ESA-PECS project No. 98030 Institutional research plan: CEZ:AV0Z10030501 Source of funding: V - iné verejné zdroje Keywords : Sun * activity * atmospheric motions Subject RIV: BN - Astronomy, Celestial Mechanics, Astrophysics Impact factor: 6.405, year: 2007

  7. Adsorption Enthalpies of Hydrogen on Chemically Enhanced Carbon Nanospaces

    Science.gov (United States)

    Gillespie, Andrew; Dohnke, Elmar; Schaeperkoetter, Joseph; Stalla, David; Pfeifer, Peter

    2014-03-01

    Chemical functionalization of carbon nanopore spaces has been shown to significantly increase the differential enthalpy of adsorption of hydrogen (ca. 9kJ/mol). This improved surface interaction corresponds to an increased density of the adsorbed film. Functionalized carbon samples have been produced through KOH activation, deposition of decaborane, and high temperature annealing. Hydrogen sorption measurements have shown significant improvements to stored film densities and binding energies. In this talk, a systematic study of the effect that boron concentration has on the samples' pore structures, binding energies, surface excess concentrations, and volumetric storage capacities is presented. Work supported by DOE-EERE, Award No. DE-FG36-08GO18142.

  8. Temperature-dependent enthalpy of oxygenation in Antarctic fish hemoglobins

    DEFF Research Database (Denmark)

    Fago, A.; Wells, R.M.G.; Weber, Roy E.

    1997-01-01

    literature data for the enthalpy of oxygenation in Antarctic fish hemoglobins derives from the use of the nonintegrated (linearized) form of the van't Hoff equation over different temperature ranges. The general assumption that a low heat of oxygenation in hemoglobins from polar animals represents......The effect of temperature on the oxygen-binding properties of the hemoglobins of three cold-adapted Antarctic fish species, Dissostichus mawsoni, Pagothenia borchgrevinki and Trematomus, sp., has been investigated under different pH values and buffer conditions. A clear non linear van't Hoff plot...

  9. Meridional gradients of light absorbing carbon over northern Europe

    International Nuclear Information System (INIS)

    Baumgardner, D; Kok, G; Kraemer, M; Weidle, F

    2008-01-01

    In situ measurements have been made in the upper troposphere of the properties of particles containing light absorbing carbon (LAC). These measurements, made in late November 2006 over northern Europe, show that the average LAC mass concentration varies between 1 and 5 ng m -3 over a latitude range 50 deg. to 70 deg. N, with maxima at 50 deg. and 66 deg. The relative fraction of all particles larger than 0.1 μm that contain LAC decreases at higher latitudes. The derived extinction coefficient, which also increases with latitude, reaches a maximum of 1.4 Mm -1 at 66 deg. The air mass histories associated with the LAC were evaluated with back trajectory analysis using wind field analysis from the European Center for Median-Range Weather Forecast (ECMWF). A positive correlation exists between the fraction of particles containing LAC and the maximum relative humidity (RH), minimum temperature and maximum number of hours of cloud experienced by the air mass in the 5-10 days prior to being sampled by the aircraft. Air masses arriving from lower altitudes and with trajectories over North America also had larger concentration fractions of LAC. The average LAC mass is in good agreement with previous measurements made over North America for the same latitude range, and the span of values fits best with model predictions of LAC distributions that assume that the LAC transported from surface sources is hydrophobic

  10. Kinetics and enthalpy of crystallization of uric acid dihydrate

    Energy Technology Data Exchange (ETDEWEB)

    Sádovská, Galina, E-mail: galina.sadovska@upce.cz; Honcová, Pavla; Sádovský, Zdeněk

    2013-08-20

    Highlights: • The kinetic constant and growth order of crystallization of uric acid dihydrate was calculated. • The equation describing first-order crystal growth was derived. • The enthalpy of crystallization of uric acid dihydrate was determined. - Abstract: The kinetics of crystallization of uric acid dihydrate in aqueous solution with a constant ionic strength 0.3 mol dm{sup −3} NaCl and at thermodynamic and physiological temperature (25 and 37 °C) was studied using isoperibolic reaction twin calorimeter. The enthalpy of crystallization Δ{sub cr}H = −47.3 ± 0.9 and −46.2 ± 1.4 kJ mol{sup −1}and kinetic constant k{sub g} = 2.0 × 10{sup −8} and 9.6 × 10{sup −8} m{sup 4} s{sup −1} mol{sup −1} were determined at 25 and 37 °C, respectively.

  11. Parabolic troughs to increase the geothermal wells flow enthalpy

    Energy Technology Data Exchange (ETDEWEB)

    Lentz, Alvaro; Almanza, Rafael [Engineering Institute, National Autonomous University of Mexico, Building 12, Cuidad Universitaria, Mexico D.F., A.P. 70-472, C.P. 04510 (Mexico)

    2006-10-15

    This work investigates the feasibility of using parabolic trough solar field to increase the enthalpy from geothermal wells' flow in order to increase the steam tons; in addition, it is possible to prevent silica deposition in the geothermal process. The high levels of irradiance in Northwestern Mexico make it possible to integrate a solar-geothermal hybrid system that uses two energy resources to provide steam for the geothermal cycle, like the Cerro Prieto geothermal field. The plant consists of a geothermal well, a parabolic trough solar field in series, flash separator, steam turbine and condenser. Well '408' of Cerro Prieto IV has enthalpy of 1566kJ/kg and its quality must be increased by 10 points, which requires a {delta}h of 194.4kJ/kg. Under these considerations the parabolic troughs area required will be 9250m{sup 2}, with a flow of 92.4tons per hour (25.67kg/s). The solar field orientation is a N-S parabolic trough concentrator. The silica content in the Cerro Prieto geothermal brine causes problems for scaling at the power facility, so scale controls must be considered. (author)

  12. Enthalpy and the mechanics of AdS black holes

    International Nuclear Information System (INIS)

    Kastor, David; Traschen, Jennie; Ray, Sourya

    2009-01-01

    We present geometric derivations of the Smarr formula for static AdS black holes and an expanded first law that includes variations in the cosmological constant. These two results are further related by a scaling argument based on Euler's theorem. The key new ingredient in the constructions is a two-form potential for the static Killing field. Surface integrals of the Killing potential determine the coefficient of the variation of Λ in the first law. This coefficient is proportional to a finite, effective volume for the region outside the AdS black hole horizon, which can also be interpreted as minus the volume excluded from a spatial slice by the black hole horizon. This effective volume also contributes to the Smarr formula. Since Λ is naturally thought of as a pressure, the new term in the first law has the form of effective volume times change in pressure that arises in the variation of the enthalpy in classical thermodynamics. This and related arguments suggest that the mass of an AdS black hole should be interpreted as the enthalpy of the spacetime.

  13. Listening to PS II: enthalpy, entropy, and volume changes.

    Science.gov (United States)

    Hou, Harvey J M; Mauzerall, David

    2011-01-01

    Photosystem II, located in the thylakoid membranes of green plants, algae, and cyanobacteria, uses sunlight to split water into protons, electrons, and a dioxygen molecule. The mechanism of its electron transfers and oxygen evolution including the structure of the protein and rates of the S-state cycle has been extensively investigated. Substantial progress has been made; however, the thermodynamics of PS II electron transfer and of the oxygen cycle are poorly understood. Recent progress in thermodynamic measurements in photosynthesis provides novel insights on the enthalpic and entropic contribution to electron transfer in proteins. In this review the thermodynamic parameters including quantum yield, enthalpy, entropy, and volume changes of PS II photochemistry determined by photoacoustics and other laser techniques are summarized and evaluated. Light-driven volume changes via electrostriction are directly related to the photoreaction in PS II and thus can be a useful measurement of PS II activity and function. The enthalpy changes of the reactions observed can be directly measured by photoacoustics. The apparent reaction entropy can also be estimated when the free energy is known. Dissecting the free energy of a photoreaction into enthalpic and entropic components provides critical information about mechanisms of PS II function. Potential limitations and future direction of the study of the thermodynamics of PS II electron transfer and oxygen evolution are presented. Published by Elsevier B.V.

  14. Relaxation of enthalpy fluctuations during sub-T(g) annealing of glassy selenium.

    Science.gov (United States)

    Gulbiten, Ozgur; Mauro, John C; Lucas, Pierre

    2013-06-28

    The relaxation behavior of glass is influenced by the presence of dynamical heterogeneities, which lead to an intrinsically non-monotonic decay of fluctuations in density and enthalpy during isothermal annealing. This is apparently a universal feature of fragile glass forming systems associated with localized spatial variations in relaxation time. Here we present direct experimental observation of the nonmonotonic evolution of enthalpy fluctuations in glassy selenium annealed near room temperature. The nonmonotonic change in the distribution of enthalpy fluctuations measured by heat capacity spectroscopy offers direct evidence for the presence of dynamical heterogeneity in this glass. An enthalpy landscape model of selenium is then used to simulate annealing under identical conditions. The simulation results closely follow the evolution of enthalpy fluctuations observed experimentally. The close match between model and experiment demonstrate that enthalpy and density fluctuations are sources of dynamical heterogeneities in glassy materials.

  15. Thermodynamic Relationship between Enthalpy of Mixing and Excess Entropy in Solid Solutions of Binary Alloys

    OpenAIRE

    Hara, Shigeta; Gokcen, Nev A.; Kumar C. Kumar; Morita, Zen-ichiro; Tanaka, Toshihiro

    1996-01-01

    Thermodynamic relationships between enthalpy of mixing and excess entropy, and partial enthalpy of solution and partial excess entropy in solid solutions of binary alloys have been derived based on the free volume theory. Using the above relations, excess entropy and excess Gibbs energy of solid solutions in Ag-Au, Ag-Pd and Au-Pd binary alloys have been calculated from enthalpy of mixing, and compared with the literature values.

  16. Using Enthalpy as a Prognostic Variable in Atmospheric Modelling with Variable Composition

    Science.gov (United States)

    2016-04-14

    InterScience (www.interscience.wiley.com) DOI: 10.1002/qj.345 Using enthalpy as a prognostic variable in atmospheric modelling with variable composition† R...Maryland, USA cNow at NOAA/NCEP, Space Weather Prediction Centre, Boulder, Colorado, USA ABSTRACT: Specific enthalpy emerges from a general form of the...trajectories depend- ing on sources, sinks, and fluxes of individual tracers. Specific enthalpy , h = cpT , (1) where cp is the specific heat capacity at

  17. Vapour pressures and enthalpies of vaporization of a series of the ferrocene derivatives

    International Nuclear Information System (INIS)

    Emel'yanenko, Vladimir N.; Verevkin, Sergey P.; Krol, Olesya V.; Varushchenko, Raisa M.; Chelovskaya, Nelly V.

    2007-01-01

    Vapour pressures of the ferrocene, ferrocene-methanol, benzyl-ferrocene, and benzoyl-ferrocene have been determined by the transpiration method. The molar enthalpies of sublimation Δ cr g H m and of vaporization Δ l g H m have been determined from the temperature dependence of the vapour pressure. The molar enthalpies of fusion of these compounds were measured by d.s.c. The measured data sets of vaporization, sublimation, and fusion enthalpies were checked for internal consistency

  18. Study on the enthalpy of solution and enthalpy of dilution for the ionic liquid [C3mim][Val] (1-propyl-3-methylimidazolium valine)

    International Nuclear Information System (INIS)

    Guan Wei; Li Long; Ma Xiaoxue; Tong Jing; Fang Dawei; Yang Jiazhen

    2012-01-01

    Graphical abstract: The thermodynamic cycle for estimation of the hydration enthalpy of ionic liquid [C 3 mim][Val]. Highlights: ► A new amino acid ionic liquid [C 3 mim][Val] was prepared. ► The molar enthalpies of solution of the ionic liquid. ► The hydration enthalpy of the cation [C 3 mim] + was estimated. ► The molar enthalpies of dilution, of aqueous [C 3 mim][Val] were measured. - Abstract: A new amino acid ionic liquid (AAIL) [C 3 mim][Val] (1-propyl-3-methylimidazolium valine) was prepared by the neutralization method. Using the solution-reaction isoperibol calorimeter, molar solution enthalpies of the ionic liquid [C 3 mim][Val] with known amounts of water and with different concentrations in molality were measured at T = 298.15 K. In terms of standard addition method (SAM) and Archer’s method, the standard molar enthalpy of solution for [C 3 mim][Val] without water, Δ s H m ∘ = (−55.7 ± 0.4) kJ · mol −1 , was obtained. The hydration enthalpy of the cation [C 3 mim] + , ΔH + ([C 3 mim] + ) = −226 kJ · mol −1 , was estimated in terms of Glasser’s theory. Using the RD496-III heat conduction microcalorimeter, the molar enthalpies of dilution, Δ D H m (m i → m f ), of aqueous [C 3 mim][Val] with various values of molality were measured. The values of Δ D H m (m i → m f ) were fitted to Pitzer’s ion-interaction model and the values of apparent relative molar enthalpy, φ L, calculated using Pitzer’s ion-interaction model.

  19. Magnetohydrdodynamic models of coronal transients in the meridional plane. IV. effect of the solar wind

    International Nuclear Information System (INIS)

    Wu, S.T.; Steinolfson, R.S.; Dryer, M.; Tandberg-Hanssen, E.

    1981-01-01

    A two-dimensional, time-dependenct magnetohydrodynamic model in the meridional plane with and without an ambient solar wind in an ambient radial magnetic field has been used to investigate mass motions associated with coronal transients. We show that that solar wind does not significantly affect the general dynamic characteristics of the mass motion. The ambient solar wind, however, increases the velocity of the mass motion and produces a moderate change in the thermodynamic properties of the coronal plasma

  20. Agrobiodiversity of cactus pear (Opuntia, Cactaceae) in the Meridional Highlands Plateau of Mexico

    OpenAIRE

    Juan Antonio Reyes-Agüero; Juan Rogelio Aguirre Rivera

    2011-01-01

    Mexico is characterized by a remarkable richness of Opuntia, mostly at the Meridional Highlands Plateau; it is also here where the greatest richness of Opuntia variants occurs. Most of these variants have been maintained in homegardens; however, the gathering process which originated these homegardens has been disrupted over the past decades, as a result of social change and the destruction of large wild nopaleras. If the variants still surviving in homegardens are lost, these will be hard to...

  1. The Emergence of the Pacific Meridional Overturning Circulation (PMOC) Paced by Obliquity Cycles during the Pliocene

    Science.gov (United States)

    Burls, N.; Fedorov, A. V.; Sigman, D. M.; Jaccard, S.; Tiedemann, R.; Haug, G. H.

    2016-12-01

    Deep water formation in northern high latitudes, as part of the Atlantic meridional overturning circulation (AMOC), is a critical element of modern ocean circulation and climate. For the warm Pliocene, roughly 4 to 2.8 million years ago, we present measurements and modeling evidence that deep water formation also occurred in the North Pacific, supporting another overturning cell - the Pacific meridional overturning circulation (PMOC). The evidence includes calcium carbonate accumulation in Pliocene subarctic Pacific sediments rivaling that of the modern North Atlantic, with pigment, total organic carbon, and redox-sensitive trace metal measurements supporting deep ocean ventilation as the driver of the enhanced calcium carbonate preservation. Together with high accumulation rates of biogenic opal, this implies a bi-directional communication between surface waters and the waters overlying the deep seafloor, and hence deep convection. A Pliocene-like climate simulation reproduces this deep water formation, with co-occurring Atlantic and Pacific overturning cells. The PMOC emerges as a result of the less intense hydrological cycle under Pliocene conditions characterized by a reduced meridional SST gradient. This weaker hydrological cycle leads to the erosion of the North Pacific halocline, allowing deep convection. Examining the data in more detail shows that, while the opal accumulation rate was continuously high, maxima in calcium carbonate accumulation rate were sharp and intermittent. Most likely, these maxima occurred during Northern Hemisphere summer insolation maxima when, as supported by the modeling results, mid-latitude SSTs in the Northern Hemisphere were at a maximum and the meridional SST gradient was particularly weak. These findings suggest that the climate system fluctuated between periods of strong and weak PMOC during the Pliocene. Such fluctuations appear to be a crucial part of Pliocene climate variability on orbital timescales.

  2. Impact of the GeoMIP G1 sunshade geoengineering experiment on the Atlantic meridional overturning circulation

    Science.gov (United States)

    Hong, Yu; Moore, John C.; Jevrejeva, Svetlana; Ji, Duoying; Phipps, Steven J.; Lenton, Andrew; Tilmes, Simone; Watanabe, Shingo; Zhao, Liyun

    2017-03-01

    We analyze the multi-earth system model responses of ocean temperatures and the Atlantic Meridional Overturning Circulation (AMOC) under an idealized solar radiation management scenario (G1) from the Geoengineering Model Intercomparison Project. All models simulate warming of the northern North Atlantic relative to no geoengineering, despite geoengineering substantially offsetting the increases in mean global ocean temperatures. Increases in the temperature of the North Atlantic Ocean at the surface (˜0.25 K) and at a depth of 500 m (˜0.10 K) are mainly due to a 10 Wm-2 reduction of total heat flux from ocean to atmosphere. Although the AMOC is slightly reduced under the solar dimming scenario, G1, relative to piControl, it is about 37% stronger than under abrupt4 × CO2 . The reduction of the AMOC under G1 is mainly a response to the heat flux change at the northern North Atlantic rather than to changes in the water flux and the wind stress. The AMOC transfers heat from tropics to high latitudes, helping to warm the high latitudes, and its strength is maintained under solar dimming rather than weakened by greenhouse gas forcing acting alone. Hence the relative reduction in high latitude ocean temperatures provided by solar radiation geoengineering, would tend to be counteracted by the correspondingly active AMOC circulation which furthermore transports warm surface waters towards the Greenland ice sheet, warming Arctic sea ice and permafrost.

  3. Agrobiodiversity of cactus pear (Opuntia, Cactaceae in the Meridional Highlands Plateau of Mexico

    Directory of Open Access Journals (Sweden)

    Juan Antonio Reyes-Agüero

    2011-08-01

    Full Text Available Mexico is characterized by a remarkable richness of Opuntia, mostly at the Meridional Highlands Plateau; it is also here where the greatest richness of Opuntia variants occurs. Most of these variants have been maintained in homegardens; however, the gathering process which originated these homegardens has been disrupted over the past decades, as a result of social change and the destruction of large wild nopaleras. If the variants still surviving in homegardens are lost, these will be hard to recover, that is, the millenary cultural heritage from the human groups that populated the Mexican Meridional Highland Plateau will be lost forever. This situation motivated the preparation of a catalogue that records the diversity of wild and cultivated Opuntia variants living in the meridional Highlands Plateau. To this end, 379 samples were obtained in 29 localities, between 1998 and 2003. The information was processed through Twinspan. All specimens were identified and preserved in herbaria. Botanical keys and descriptions were elaborated. The catalogue includes information on 126 variants comprising 18 species. There were species with only one variant (Opuntia atropes, O. cochinera, O. jaliscana, O. leucotricha, O. rzedowskii and O. velutina, two (O. durangensis, O. lindheimeri, O. phaeacantha and O. robusta, five (O. joconostle and O. lasiacantha, seven (O. chavena, 12 (O. hyptiacantha and O. streptacantha, 15 (O. ficus-indica, 22 (O. albicarpa, and up to 34 (O. megacantha. Additionally, 267 common cactus pear names were related to those variants.

  4. Evidence that a Deep Meridional Flow Sets the Sunspot Cycle Period

    Science.gov (United States)

    Hathaway, David H.; Nandy, D.; Wilson, R. M.; Reichmann, E. J.

    2003-01-01

    Sunspots appear on the Sun in two bands on either side of the equator that drift toward lower latitudes as each sunspot cycle progresses. We examine the equatorward drift of the centroid of the sunspot area in each hemisphere from 1874 to 2002 and find that the drift rate slows as the centroid approaches the equator. We compare the drift rate at sunspot cycle maximum to the cycle-period for each hemisphere and find a highly significant anti-correlation: hemispheres with faster drift rates have shorter periods. These observations are. consistent with an equatorward meridional counterflow, deep within the Sun, as the primary driver of the equatorward migration and the period associated with the sunspot cycle. We also find that the drift rate at maximum is significantly correlated with the amplitude of the following cycle, a prediction of dynamo models that employ a deep equatorward meridional flow. Our results indicate an amplitude of about 1.2 m/s for the meridional flow velocity at the base of the solar convection zone.

  5. Wind Diffusivity Current, QuikSCAT SeaWinds, 0.25 degrees, Global, Science Quality, Meridional

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — NOAA CoastWatch distributes science quality Ekman current (in zonal, meridional, and modulus sets) and Ekman upwelling data. This data begins with wind velocity...

  6. Intra-seasonal Oscillations (ISO of zonal-mean meridional winds and temperatures as measured by UARS

    Directory of Open Access Journals (Sweden)

    F. T. Huang

    2005-06-01

    Full Text Available Based on an empirical analysis of measurements with the High Resolution Doppler Imager (HRDI on the UARS spacecraft in the upper mesosphere (95km, persistent and regular intra-seasonal oscillations (ISO with periods of about 2 to 4 months have recently been reported in the zonal-mean meridional winds. Similar oscillations have also been discussed independently in a modeling study, and they were attributed to wave-mean-flow interactions. The observed and modeled meridional wind ISOs were largely confined to low latitudes. We report here on an analysis of concurrent UARS temperature measurements, which produces oscillations similar to those seen in the meridional winds. Although the temperature oscillations are observed at lower altitudes (55km, their phase variations with latitude are qualitatively consistent with the inferred properties seen in the meridional winds and thus provide independent evidence for the existence of ISOs in the mesosphere.

  7. Characteristics of low-enthalpy geothermal applications in Greece

    Energy Technology Data Exchange (ETDEWEB)

    Andritsos, N. [Department of Mechanical Engineering, University of Thessaly, Pedion Areos, 383 34 Volos (Greece); Dalabakis, P. [Land Reclamation Institute, NAGREF, 574 00 Sindos, Thessaloniki (Greece); Karydakis, G. [IGME, Geothermal Energy Section, Sp. Loui 1, 136 77 Acharnes (Greece); Kolios, N. [IGME, Branch of Central Macedonia, Frangon 1, 546 26 Thessaloniki (Greece); Fytikas, M. [Department of Geology, Aristotle University of Thessaloniki, 540 06 Thessaloniki (Greece)

    2011-04-15

    The paper offers a brief overview of the current direct geothermal uses in Greece and discusses their characteristics, with emphasis to the economical and technical problems encountered. Greece holds a prominent place in Europe regarding the existence of promising geothermal resources (both high and low-enthalpy), which can be economically exploited. Currently, no geothermal electricity is produced in Greece. The installed capacity of direct uses at the end of 2009 is estimated at about 155 MW{sub t}, exhibiting an increase of more than 100% compared to the figures reported at the World Geothermal Congress 2005. The main uses, in decreasing share, are geothermal heat pumps, swimming and balneology, greenhouse heating and soil warming. Earth-coupled and groundwater (or seawater) heat pumps have shown a drastic expansion during the past 2-3 years, mainly due to high oil prices two years ago and easing of the license requirements for drilling shallow wells. (author)

  8. Changes of enthalpy slope in subcooled flow boiling

    Energy Technology Data Exchange (ETDEWEB)

    Collado, Francisco J.; Monne, Carlos [Universidad de Zaragoza-CPS, Departamento de Ingenieria Mecanica-Motores Termicos, Zaragoza (Spain); Pascau, Antonio [Universidad de Zaragoza-CPS, Departamento de Ciencia de los Materiales y Fluidos-Mecanica de Fluidos, Zaragoza (Spain)

    2006-03-01

    Void fraction data in subcooled flow boiling of water at low pressure measured by General Electric in the 1960s are analyzed following the classical model of Griffith et al. (in Proceedings of ASME-AIChE heat transfer conference, 58-HT-19, 1958). In addition, a new proposal for analyzing one-dimensional steady flow boiling is used. This is based on the physical fact that if the two phases have different velocities, they cannot cover the same distance - the control volume length - in the same time. So a slight modification of the heat balance is suggested, i.e., the explicit inclusion of the vapor-liquid velocity ratio or slip ratio as scaling time factor between the phases, which is successfully checked against the data. Finally, the prediction of void fraction using correlations of the net rate of change of vapor enthalpy in the fully developed regime of subcooled flow boiling is explored. (orig.)

  9. Molecular rigidity and enthalpy-entropy compensation in DNA melting.

    Science.gov (United States)

    Vargas-Lara, Fernando; Starr, Francis W; Douglas, Jack F

    2017-11-15

    Enthalpy-entropy compensation (EEC) is observed in diverse molecular binding processes of importance to living systems and manufacturing applications, but this widely occurring phenomenon is not sufficiently understood from a molecular physics standpoint. To gain insight into this fundamental problem, we focus on the melting of double-stranded DNA (dsDNA) since measurements exhibiting EEC are extensive for nucleic acid complexes and existing coarse-grained models of DNA allow us to explore the influence of changes in molecular parameters on the energetic parameters by using molecular dynamics simulations. Previous experimental and computational studies have indicated a correlation between EEC and changes in molecular rigidity in certain binding-unbinding processes, and, correspondingly, we estimate measures of DNA molecular rigidity under a wide range of conditions, along with resultant changes in the enthalpy and entropy of binding. In particular, we consider variations in dsDNA rigidity that arise from changes of intrinsic molecular rigidity such as varying the associative interaction strength between the DNA bases, the length of the DNA chains, and the bending stiffness of the individual DNA chains. We also consider extrinsic changes of molecular rigidity arising from the addition of polymer additives and geometrical confinement of DNA between parallel plates. All our computations confirm EEC and indicate that this phenomenon is indeed highly correlated with changes in molecular rigidity. However, two distinct patterns relating to how DNA rigidity influences the entropy of association emerge from our analysis. Increasing the intrinsic DNA rigidity increases the entropy of binding, but increases in molecular rigidity from external constraints decreases the entropy of binding. EEC arises in numerous synthetic and biological binding processes and we suggest that changes in molecular rigidity might provide a common origin of this ubiquitous phenomenon in the mutual

  10. Effect of cure cycle on enthalpy relaxation and post shrinkage in neat epoxy and epoxy composites

    DEFF Research Database (Denmark)

    Jensen, Martin; Jakobsen, Johnny

    2016-01-01

    The effect of cure cycle on enthalpy relaxation and warpage is studied for both neat epoxy and glass/epoxy composites. An approach for determining the enthalpy relaxation in the matrix of composite materials combining modulated differential scanning calorimetry and thermogravimetry is presented...

  11. Effect of Calcium chloride and Cadmium chloride on the enthalpy of ...

    African Journals Online (AJOL)

    This paper presents the effect of two dissolved inorganic salts, CaCl2 and CdCl2 on the enthalpy of mixing of the binary 1,4 dioxane + water system has been investigated at 303.15 K in an isothermal displacement calorimeter with vapour space. A significantly increasing trend in the endothermic excess enthalpy values for ...

  12. Enthalpy Costs of Making and Breaking Bonds: A Game of Generating Molecules with Proper Lewis Structures

    Science.gov (United States)

    Bell, Peter T.; Adkins, Alyssa D.; Gamble, Rex J.; Schultz, Linda D.

    2009-01-01

    "Enthalpy Costs" is a simple card game created to assist students in developing proper Lewis structure drawing skills. Score keeping is accomplished by tracking the enthalpy changes associated with bond-making and bond-breaking processes during formation of molecules represented by proper Lewis structures. Playing the game requires the student to…

  13. Effect of Calcium chloride and Cadmium chloride on the enthalpy of ...

    African Journals Online (AJOL)

    user

    Enthalpy of mixing of methanol + benzene + mercuric chloride at 303.15 K, Journal of Chemical Engineering Data, Vol.44, pp248- 250. Dharmendira Kumar. M. and Rajendran. M. 1999. Salt effect on enthalpy of mixing of water + methanol at 303.15 K, Fluid Phase. Equilibria, Vol.164, pp. 217-224. Furter.W.F. and Cook.

  14. Thermochemical study of 1-acetyl vinyl p-nitrobenzoate: vinyl bond enthalpy in captodative olefins.

    Science.gov (United States)

    Rojas, Aarón; Valdés-Ordoñez, Alejandro; Martínez-Herrera, Melchor; Torres, Luis Alfonso; Campos, Myriam; Hernández-Obregón, Javier; Herrera, Rafael; Tamariz, Joaquín

    2015-05-21

    Captodative olefins are highly reactive and selective substrates in Diels-Alder and 1,3-dipolar cycloadditions. Seeking an explanation of this fact based on molecular energetics, the thermochemical analysis of 1-acetyl vinyl p-nitrobenzoate, a captodative olefin, has been performed using semi-micro-combustion calorimetry, effusion measurements through a quartz crystal microbalance, and differential scanning calorimetry. The molar standard combustion energy and enthalpy as well as the molar standard formation enthalpy are reported along with sublimation and melting enthalpies. From these data, experimental formation enthalpy of the gas-phase is derived and compared with the theoretical value calculated through the density functional theory procedure. The olefinic bond enthalpy is also computed from experimental data, and the relevance of the results is discussed.

  15. Bulk Enthalpy Calculations in the Arc Jet Facility at NASA ARC

    Science.gov (United States)

    Thompson, Corinna S.; Prabhu, Dinesh; Terrazas-Salinas, Imelda; Mach, Jeffrey J.

    2011-01-01

    The Arc Jet Facilities at NASA Ames Research Center generate test streams with enthalpies ranging from 5 MJ/kg to 25 MJ/kg. The present work describes a rigorous method, based on equilibrium thermodynamics, for calculating the bulk enthalpy of the flow produced in two of these facilities. The motivation for this work is to determine a dimensionally-correct formula for calculating the bulk enthalpy that is at least as accurate as the conventional formulas that are currently used. Unlike previous methods, the new method accounts for the amount of argon that is present in the flow. Comparisons are made with bulk enthalpies computed from an energy balance method. An analysis of primary facility operating parameters and their associated uncertainties is presented in order to further validate the enthalpy calculations reported herein.

  16. Excess molar enthalpies for binary mixtures of different amines with water

    International Nuclear Information System (INIS)

    Zhang, Ruilei; Chen, Jian; Mi, Jianguo

    2015-01-01

    Highlights: • Isothermal excess molar enthalpies for binary mixtures of different amines with water. • The Redlich–Kister equation and the NRTL model was used to fit the experimental data. • The excess molar enthalpies were discussed with different structures of amines. - Abstract: The isothermal excess molar enthalpies for binary mixtures of different amines with water were measured with a C-80 Setaram calorimeter. The experimental results indicate that the excess molar enthalpy is related to the molecular structure. The experimental excess molar enthalpies were satisfactorily fitted with the Redlich–Kister equation. They were also used to test the suitability of the NRTL model, and the deviations are a little larger than the R–K equation

  17. COTHERM: Geophysical Modeling of High Enthalpy Geothermal Systems

    Science.gov (United States)

    Grab, Melchior; Maurer, Hansruedi; Greenhalgh, Stewart

    2014-05-01

    In recent years geothermal heating and electricity generation have become an attractive alternative energy resource, especially natural high enthalpy geothermal systems such as in Iceland. However, the financial risk of installing and operating geothermal power plants is still high and more needs to be known about the geothermal processes and state of the reservoir in the subsurface. A powerful tool for probing the underground system structure is provided by geophysical techniques, which are able to detect flow paths and fracture systems without drilling. It has been amply demonstrated that small-scale features can be well imaged at shallow depths, but only gross structures can be delineated for depths of several kilometers, where most high enthalpy systems are located. Therefore a major goal of our study is to improve geophysical mapping strategies by multi-method geophysical simulations and synthetic data inversions, to better resolve structures at greater depth, characterize the reservoir and monitor any changes within it. The investigation forms part of project COTHERM - COmbined hydrological, geochemical and geophysical modeling of geoTHERMal systems - in which a holistic and synergistic approach is being adopted to achieve multidisciplinary cooperation and mutual benefit. The geophysical simulations are being performed in combination with hydrothermal fluid flow modeling and chemical fluid rock interaction modeling, to provide realistic constraints on lithology, pressure, temperature and fluid conditions of the subsurface. Two sites in Iceland have been selected for the study, Krafla and Reykjanes. As a starting point for the geophysical modeling, we seek to establish petrophysical relations, connecting rock properties and reservoir conditions with geophysical parameters such as seismic wave speed, attenuation, electrical conductivity and magnetic susceptibility with a main focus on seismic properties. Therefore, we follow a comprehensive approach involving

  18. Meridional flow and differential rotation by gravity darkening in fast rotating solar-type stars

    Science.gov (United States)

    Rüdiger, G.; Küker, M.

    2002-04-01

    An explanation is presented for the rather strong total surface differential rotation of the observed very young solar-type stars like AB Dor and PZ Tel. Due to its rapid rotation, a non-uniform energy flux leaves the stellar core so that the outer convection zone is non-uniformly heated from below. Due to this ``gravity darkening'' of the equator, a meridional flow is created flowing equatorwards at the surface and thus accelerating the equatorial rotation. The effect linearly grows with the normalized pole-equator difference, epsilon , of the heat-flux at the bottom of the convection zone. A rotation rate of about 9 h leads to epsilon =0.1 for a solar-type star. In this case the resulting equator-pole differences of the angular velocity at the stellar surface, delta Omega , varies from unobservable 0.005 day-1 to the (desired) value of 0.03 day-1 when the dimensionless diffusivity factors cnu and cchi vary between 1 and 0.1 (standard value cnu =~ cchi =~ 0.3, see Table \\ref{tab1}). In all cases the related temperature differences between pole and equator at the surface are unobservably small. The (clockwise) meridional circulation which we obtain flows opposite to the (counterclockwise) circulation appearing as a byproduct in the Lambda -theory of the non-uniform rotation in outer convection zones. The consequences of this situation for those dynamo theories of stellar activity are discussed that work with the meridional circulation as the dominant magnetic-advection effect in latitude to produce the solar-like form of the butterfly diagram.

  19. Controls on the meridional extent of tropical precipitation and its contraction under global warming

    Science.gov (United States)

    Donohoe, A.

    2017-12-01

    A method for decomposing changes and variability in the spatial structure of tropical precipitation into shifting (meridional translation), contracting, and intensifying modes of variability is introduced. We demonstrate that the shifting mode of tropical precipitation explains very little (20%) more of the tropical precipitation changes and variability. Furthermore, the contraction of tropical precipitation is highly correlated (R2 > 0.95) with an intensification of the precipitation in both the observations and forced modeled simulations. These results suggest that the simultaneous contraction and intensification of tropical precipitation is the dominant mode of variability and changes under external forcing. We speculate that tropical surface temperature controls this concurrent variability. Indeed, models robustly predict that tropical precipitation increases and meridionally contracts in response to increased CO2 and is reduced and meridionally expanded under glacial forcing and boundary conditions. In contrast, the directionality of the tropical precipitation shift is both ambiguous and small in magnitude in response to increased CO2. Furthermore, the ratio of the contraction/expansion to intensification/reduction is consistent in the continuum of climate states from the glacial climate to a modern climate to a 4XCO2 climate suggesting that the intensification and contraction are linked together via a single mechanism. We examine two mechanisms responsible for the contraction of the precipitation under global warming : i. the reduction of the seasonal cycle of energy input to the atmosphere due to sea ice retreat that results in the tropical precipitation remaining closer to the equator during the solsticial seasons and; ii. the increased gross moist stability of the tropical atmosphere as the surface warms resulting in a weaker cross-equatorial Hadley circulation during the solsticial seasons.

  20. Oxygen variability and meridional oxygen supply in the tropical North East Atlantic oxygen minimum zone

    Science.gov (United States)

    Hahn, Johannes; Brandt, Peter; Greatbatch, Richard J.; Krahmann, Gerd; Körtzinger, Arne

    2013-04-01

    The oxygen minimum zone (OMZ) of the tropical North East Atlantic (TNEA) is located between the oxygen-rich equatorial region and the Cape Verde Frontal Zone at about 20°N in a depth range of 300 - 700 m. Its horizontal extent is predominantly defined by the North Equatorial Current and by the equatorial zonal current system ventilating the region to the north and south of the OMZ, respectively. The interior of the OMZ is characterized by a sluggish flow regime, where mesoscale eddies play a major role in the ventilation. In this study we focus on the oxygen variability in the TNEA as well as the eddy driven lateral ventilation of the TNEA OMZ across its southern boundary. During recent years an intense measurement program was executed along 23°W cutting meridionally through the TNEA OMZ. Hydrographic and velocity data has been acquired from ship sections and moorings, together covering the latitude range between 6°S and 14°N with particularly high meridional resolution of shipboard and high temporal resolution of moored observations. Based on shipboard data we derived a meridional section of oxygen variance, which reveals numerous local maxima of oxygen variability. Exemplary, strong oxygen variability is observed at the upper (300m, 5° - 12°N) and the southern boundary (400m - 700m, 5°N - 8°N) of the OMZ, whereas the interior of the OMZ is characterized by weak variability. An application of the extended Osborn-Cox model shows that the strong oxygen variability at the southern boundary is mainly generated by mesoscale eddies. The strong variability at the upper boundary is generated by mesoscale eddies as well as microscale turbulence. We apply two methods to estimate the meridional oxygen flux: 1) a flux gradient parameterization and 2) a correlation of oxygen and velocity mooring time series. From the analysis of the 5°N mooring data we find a northward oxygen flux directed towards the OMZ at its core depth, that is mainly due to variability of

  1. Intensification of the meridional temperature gradient in the Great Barrier Reef following the Last Glacial Maximum

    OpenAIRE

    Felis, Thomas; McGregor, Helen V.; Linsley, Braddock K.; Tudhope, Alexander; Gagan, M. K.; Suzuki, Atsushi; Inoue, Mayuri; Thomas, Alex; Esat, T. M.; Thompson, William G.; Tiwari, Manish; Potts, Don; Mudelsee, Manfred; Yokoyama, Y.; Webster, Jody M.

    2014-01-01

    Tropical south-western Pacific temperatures are of vital importance to the Great Barrier Reef (GBR), but the role of sea surface temperatures (SSTs) in the growth of the GBR since the Last Glacial Maximum remains largely unknown. Here we present records of Sr/Ca and d18O for Last Glacial Maximum and deglacial corals that show a considerably steeper meridional SST gradient than the present day in the central GBR. We find a 1–2 C larger temperaturedecrease between 17 and 20S about 20,000 to 13,...

  2. Determination of the free enthalpies of formation of borosilicate glasses

    International Nuclear Information System (INIS)

    Linard, Y.

    2000-01-01

    This work contributes to the study of the thermochemical properties of nuclear waste glasses. Results are used to discuss mechanisms and parameters integrated in alteration models of conditioning materials. Glass is a disordered material defined thermodynamically as a non-equilibrium state. Taking into account one order parameter to characterise its configurational state, the metastable equilibrium for the glass was considered and the main thermochemical properties were determined. Calorimetric techniques were used to measure heat capacities and formation enthalpies of borosilicate glasses (from 3 to 8 constitutive oxides). Formation Entropies were measured too, using the entropy theory of relaxation processes proposed by Adam and Gibbs (1965). The configurational entropy contribution were determined from viscosity measurements. This set of data has allowed the calculation of Gibb's free energies of dissolution of glasses in pure water. By comparison with leaching experiments, it has been demonstrated that the decreasing of the dissolution rate at high reaction progress cannot be associated to the approach of an equilibrium between the sound glass and the aqueous solution. The composition changes of the reaction area at the glass surface need to be considered too. To achieve a complete description of the thermodynamic stability, the equilibrium between hydrated de-alkalinized glass and/or the gel layer with the aqueous solution should also be evaluated. (author)

  3. Enthalpies of combustion of two bis(N,N-diethylthioureas)

    International Nuclear Information System (INIS)

    Ribeiro da Silva, Manuel A.V.; Santos, Luis M.N.B.F.; Schroeder, Bernd; Beyer, Lothar; Dietze, Frank

    2007-01-01

    The standard (p o =0.1MPa) molar energies of combustion in oxygen, at T=298.15K, of two crystalline bis(N,N-diethylthioureas) R(CONHCSNEt 2 ) 2 : pyridine-2,6-dicarbonyl-bis(N,N-diethylthiourea), R=pyridyl , abbreviated as (bis-py-DETU), and adipoyl-dicarbonyl-bis(N,N-diethylthiourea), R=(CH 2 ) 4 , abbreviated as (bis-ad-DETU), were measured by rotating bomb calorimetry so, the standard molar enthalpies of formation of both compounds, in their crystalline phase, were derived. Compound-Δ c U m o (cr)-Δ f H m o (cr)kJ.mol -1 kJ.mol -1 Pyridine-2,6-dicarbonyl-bis(N,N -diethylthiourea) [bis-py-DETU]11027.1+/-5.2425.2+/-5.6Adipoyl-dicarbonyl-bis (N,N-diethylthiourea) [bis-ad-DETU]11124.6+/-5.7644.4+/-6.1Furthermore, the energetics of the title compounds were studied by means of density functional theory calculations at the B3LYP/ 6-311G(dp) level of theory.

  4. Enthalpy-entropy compensation effect on adsorption of light hydrocarbons on monolithic stationary phases.

    Science.gov (United States)

    Korolev, Alexander A; Shiryaeva, Valeria E; Popova, Tamara P; Kurganov, Alexander A

    2011-08-01

    Enthalpy and entropy of adsorption of light hydrocarbons C1-C4 have been measured for three monoliths of different polarity and for five different carrier gases: helium, hydrogen, nitrogen, carbon dioxide and dinitrogen oxide. Using carrier gas helium the highest values of enthalpy and entropy were observed for monolith based on ethylenedimethacrylate and the lowest values were observed for monolith based on silica, while monolith based on divinylbenzene demonstrated intermediate values. Entropy-enthalpy correlations were observed with carrier gas helium for all thee monoliths and possess similar slope indicating similar adsorption mechanism on all monoliths studied. Comparing different carrier gases entropy-enthalpy correlations within a homological series of solutes were observed for light carrier gases (He, H2 and N2) and were not observed for heavy carrier gases (CO2 and N2O). Instead, entropy-enthalpy correlations for heavy carrier gases were observed with pressure as variable and the higher the carrier gas pressure the lower the values of enthalpy and entropy observed. The observed changes in entropy-enthalpy correlations were explained by competitive adsorption of heavy carrier gas on monoliths. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Ionic liquids: differential scanning calorimetry as a new indirect method for determination of vaporization enthalpies.

    Science.gov (United States)

    Verevkin, Sergey P; Emel'yanenko, Vladimir N; Zaitsau, Dzmitry H; Ralys, Ricardas V; Schick, Christoph

    2012-04-12

    Differential scanning calorimetry (DSC) has been used to measure enthalpies of synthesis reactions of the 1-alkyl-3-methylimidazolium bromide [C(n)mim][Br] ionic liquids from 1-methylimidazole and n-alkyl bromides (with n = 4, 5, 6, 7, and 8). The optimal experimental conditions have been elaborated. Enthalpies of formation of these ionic liquids in the liquid state have been determined using the DSC results according to the Hess Law. The ideal-gas enthalpies of formation of [C(n)mim][Br] were calculated using the methods of quantum chemistry. They were used together with the DSC results to derive indirectly the enthalpies of vaporization of the ionic liquids under study. In order to validate the indirect determination, the experimental vaporization enthalpy of [C(4)mim][Br] was measured by using a quartz crystal microbalance (QCM). The combination of reaction enthalpy measurements by DSC with modern high-level first-principles calculations opens valuable indirect thermochemical options to obtain values of vaporization enthalpies of ionic liquids.

  6. New experimental heat capacity and enthalpy of formation of lithium cobalt oxide

    International Nuclear Information System (INIS)

    Gotcu-Freis, Petronela; Cupid, Damian M.; Rohde, Magnus; Seifert, Hans J.

    2015-01-01

    Highlights: • LiCoO 2 heat capacity was measured in the temperature range (160 to 953) K using DSC. • Continuous/discontinuous methods were applied on different types of calorimeters. • Enthalpy increment of LiCoO 2 was determined using drop calorimetry at T = 974 K. • Enthalpies of formation were evaluated from oxide melt drop solution calorimetry. - Abstract: The heat capacity of LiCoO 2 (O3-phase), constituent material in cathodes for lithium-ion batteries, was measured using two differential scanning calorimeters over the temperature range from (160 to 953) K (continuous method). As an alternative, the discontinuous method was employed over the temperature range from (493 to 693) K using a third calorimeter. Based on the results obtained, the enthalpy increment of LiCoO 2 was derived from T = 298.15 K up to 974.15 K. Very good agreement was obtained between the derived enthalpy increment and our independent measurements of enthalpy increment using transposed temperature drop calorimetry at 974.15 K. In addition, values of the enthalpy of formation of LiCoO 2 from the constituent oxides and elements were assessed based on measurements of enthalpy of dissolution using high temperature oxide melt drop solution calorimetry. The high temperature values obtained by these measurements are key input data in safety analysis and optimisation of the battery management systems which accounts for possible thermal runaway events

  7. Extension of the segment-based Wilson and NRTL models for correlation of excess molar enthalpies of polymer solutions

    International Nuclear Information System (INIS)

    Sadeghi, Rahmat

    2005-01-01

    The polymer Wilson model and the polymer NRTL model have been extended for the representation of the excess enthalpy of multicomponent polymer solutions. Applicability of obtained equations in the correlation of the excess enthalpies of polymer solutions has been examined. It is found that the both models are suitable models in representing the published excess enthalpy data for the tested polymer solutions

  8. A Non-Isothermal Chemical Lattice Boltzmann Model Incorporating Thermal Reaction Kinetics and Enthalpy Changes

    Directory of Open Access Journals (Sweden)

    Stuart Bartlett

    2017-08-01

    Full Text Available The lattice Boltzmann method is an efficient computational fluid dynamics technique that can accurately model a broad range of complex systems. As well as single-phase fluids, it can simulate thermohydrodynamic systems and passive scalar advection. In recent years, it also gained attention as a means of simulating chemical phenomena, as interest in self-organization processes increased. This paper will present a widely-used and versatile lattice Boltzmann model that can simultaneously incorporate fluid dynamics, heat transfer, buoyancy-driven convection, passive scalar advection, chemical reactions and enthalpy changes. All of these effects interact in a physically accurate framework that is simple to code and readily parallelizable. As well as a complete description of the model equations, several example systems will be presented in order to demonstrate the accuracy and versatility of the method. New simulations, which analyzed the effect of a reversible reaction on the transport properties of a convecting fluid, will also be described in detail. This extra chemical degree of freedom was utilized by the system to augment its net heat flux. The numerical method outlined in this paper can be readily deployed for a vast range of complex flow problems, spanning a variety of scientific disciplines.

  9. Accounting for apparent deviations between calorimetric and van't Hoff enthalpies.

    Science.gov (United States)

    Kantonen, Samuel A; Henriksen, Niel M; Gilson, Michael K

    2018-03-01

    In theory, binding enthalpies directly obtained from calorimetry (such as ITC) and the temperature dependence of the binding free energy (van't Hoff method) should agree. However, previous studies have often found them to be discrepant. Experimental binding enthalpies (both calorimetric and van't Hoff) are obtained for two host-guest pairs using ITC, and the discrepancy between the two enthalpies is examined. Modeling of artificial ITC data is also used to examine how different sources of error propagate to both types of binding enthalpies. For the host-guest pairs examined here, good agreement, to within about 0.4kcal/mol, is obtained between the two enthalpies. Additionally, using artificial data, we find that different sources of error propagate to either enthalpy uniquely, with concentration error and heat error propagating primarily to calorimetric and van't Hoff enthalpies, respectively. With modern calorimeters, good agreement between van't Hoff and calorimetric enthalpies should be achievable, barring issues due to non-ideality or unanticipated measurement pathologies. Indeed, disagreement between the two can serve as a flag for error-prone datasets. A review of the underlying theory supports the expectation that these two quantities should be in agreement. We address and arguably resolve long-standing questions regarding the relationship between calorimetric and van't Hoff enthalpies. In addition, we show that comparison of these two quantities can be used as an internal consistency check of a calorimetry study. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Behavior of the Enthalpy of Adsorption in Nanoporous Materials Close to Saturation Conditions.

    Science.gov (United States)

    Torres-Knoop, Ariana; Poursaeidesfahani, Ali; Vlugt, Thijs J H; Dubbeldam, David

    2017-07-11

    Many important industrial separation processes based on adsorption operate close to saturation. In this regime, the underlying adsorption processes are mostly driven by entropic forces. At equilibrium, the entropy of adsorption is closely related to the enthalpy of adsorption. Thus, studying the behavior of the enthalpy of adsorption as a function of loading is fundamental to understanding separation processes. Unfortunately, close to saturation, the enthalpy of adsorption is hard to measure experimentally and hard to compute in simulations. In simulations, the enthalpy of adsorption is usually obtained from energy/particle fluctuations in the grand-canonical ensemble, but this methodology is hampered by vanishing insertions/deletions at high loading. To investigate the fundamental behavior of the enthalpy and entropy of adsorption at high loading, we develop a simplistic model of adsorption in a channel and show that at saturation the enthalpy of adsorption diverges to large positive values due to repulsive intermolecular interactions. However, there are many systems that can avoid repulsive intermolecular interactions and hence do not show this drastic increase in enthalpy of adsorption close to saturation. We find that the conventional grand-canonical Monte Carlo method is incapable of determining the enthalpy of adsorption from energy/particle fluctuations at high loading. Here, we show that by using the continuous fractional component Monte Carlo, the enthalpy of adsorption close to saturation conditions can be reliably obtained from the energy/particle fluctuations in the grand-canonical ensemble. The best method to study properties at saturation is the NVT energy (local-) slope methodology.

  11. Meridional lenticular astigmatism associated with bilateral concurrent uveal metastases in renal cell carcinoma

    Directory of Open Access Journals (Sweden)

    Priluck JC

    2012-11-01

    Full Text Available Joshua C Priluck, Sandeep Grover, KV ChalamDepartment of Ophthalmology, University of Florida College of Medicine, Jacksonville, FL, USAPurpose: To demonstrate a case illustrating meridional lenticular astigmatism as a result of renal cell carcinoma uveal metastases.Methods: Case report with images.Results: Clinical findings and diagnostic testing of a patient with acquired meridional lenticular astigmatism are described. The refraction revealed best-corrected visual acuity of 20/20–1 OD (−2.50 + 0.25 × 090 and 20/50 OS (−8.25 + 3.25 × 075. Bilateral concurrent renal cell carcinoma metastases to the choroid and ciliary body are demonstrated by utilizing ultrasonography, ultrawidefield fluorescein angiography, and unique spectral-domain optical coherence tomography.Conclusions: Metastatic disease should be included in the differential of acquired astigmatism. Spectral-domain optical coherence tomography, ultrawidefield fluorescein angiography, and ultrasonography have roles in delineating choroidal metastases.Keywords: astigmatism, metastasis, optical coherence tomography, renal cell carcinoma

  12. An electrical analogy relating the Atlantic multidecadal oscillation to the Atlantic meridional overturning circulation.

    Directory of Open Access Journals (Sweden)

    Bruce E Kurtz

    Full Text Available The Atlantic meridional overturning circulation (AMOC is the northward flow of surface water to subpolar latitudes where deepwater is formed, balanced by southward abyssal flow and upwelling in the vicinity of the Southern Ocean. It is generally accepted that AMOC flow oscillates with a period of 60-80 years, creating a regular variation in North Atlantic sea surface temperature known as the Atlantic multidecadal oscillation (AMO. This article attempts to answer two questions: how is the AMOC driven and why does it oscillate? Using methods commonly employed by chemical engineers for analyzing processes involving flowing liquids, apparently not previously applied to trying to understand the AMOC, an equation is developed for AMOC flow as a function of the meridional density gradient or the corresponding temperature gradient. The equation is based on the similarity between the AMOC and an industrial thermosyphon loop cooler, which circulates a heat transfer liquid without using a mechanical pump. Extending this equation with an analogy between the flow of heat and electricity explains why the AMOC flow oscillates and what determines its period. Calculated values for AMOC flow and AMO oscillation period are in good agreement with measured values.

  13. Meridional distribution and seasonal variation of stable oxygen isotope ratio of precipitation in the Southern Ocean

    Directory of Open Access Journals (Sweden)

    Kayo Nakamura

    2010-07-01

    Full Text Available The stable oxygen isotope ratio(δ^O in precipitation is known to have important meridional and seasonal variations, but there are almost no measurements of δ^O in precipitation over polar oceans. The present research took advantage of 4 opportunities for in situ observations in summer and winter at high latitudes in the Southern Ocean. In addition, we analyzed samples of precipitation at Syowa Station in 2008 to obtain year-round data. Based on these data, we consider the meridional and seasonal variations of δ^O in precipitation over the Southern Ocean. In general, δ^O decreases with increasing latitude, and is lower in winter than in summer. The latitude gradient is stronger in winter. At 60°S, δ^O is -5.4‰ and -11.3‰ in summer and winter, respectively, while the corresponding figures at 66°S are -10.5‰ and -20.8‰. These results will help us understand the mechanisms of the salinity distribution and its variation in the Antarctic Ocean.

  14. Intensification of the meridional temperature gradient in the Great Barrier Reef following the Last Glacial Maximum

    Science.gov (United States)

    Felis, Thomas; McGregor, Helen V.; Linsley, Braddock K.; Tudhope, Alexander W.; Gagan, Michael K.; Suzuki, Atsushi; Inoue, Mayuri; Thomas, Alexander L.; Esat, Tezer M.; Thompson, William G.; Tiwari, Manish; Potts, Donald C.; Mudelsee, Manfred; Yokoyama, Yusuke; Webster, Jody M.

    2014-01-01

    Tropical south-western Pacific temperatures are of vital importance to the Great Barrier Reef (GBR), but the role of sea surface temperatures (SSTs) in the growth of the GBR since the Last Glacial Maximum remains largely unknown. Here we present records of Sr/Ca and δ18O for Last Glacial Maximum and deglacial corals that show a considerably steeper meridional SST gradient than the present day in the central GBR. We find a 1–2 °C larger temperature decrease between 17° and 20°S about 20,000 to 13,000 years ago. The result is best explained by the northward expansion of cooler subtropical waters due to a weakening of the South Pacific gyre and East Australian Current. Our findings indicate that the GBR experienced substantial meridional temperature change during the last deglaciation, and serve to explain anomalous deglacial drying of northeastern Australia. Overall, the GBR developed through significant SST change and may be more resilient than previously thought. PMID:24937320

  15. Erratum: Evidence That a Deep Meridional Flow Sets the Sunspot Cycle Period

    Science.gov (United States)

    Hathaway, David H.; Nandy, Dibyendu; Wilson, Robert M.; Reichmann, Edwin J.

    2004-01-01

    An error was made in entering the data. This changes the results concerning the length of the time lag between the variations in the meridional flow speed and those in the cycle amplitude. The final paragraph on page 667 should read: Finally, we study the relationship between the drift velocities and the amplitudes of the hemisphere/cycles. We compare the drift velocity at the maximum of the cycle to the amplitude of that cycle for that hemisphere. There is a positive (0.5) and significant (95%) correlation between the two. However, an even stronger relationship is found between the drift velocity and the amplitude of the N + 2 cycle. The correlation is stronger (0.7) and more significant (99%), as shown. This relationship is suggestive of a "memory" in the solar cycle, again a property of dynamo models that use meridional circulation. Indeed, the two-cycle lag is precisely the relationship found by Charbonneau & Dikpati. This behavior is, however, more difficult to interpret, and we elaborate on this in the next section. In either case, these correlations only explain part of the variance in cycle amplitude (25% for the current cycle and 50% for the N + 2 cycle). Obviously, other mechanisms, such as variations in the gradient in the rotation rate, also contribute to the cycle amplitude variations. Our investigation of possible connections between drift rates and the amplitudes of the N + 1 and N + 3 cycles gives no significant correlations at these alternative time lags.

  16. Insights on activation enthalpy for non-Schmid slip in body-centered cubic metals

    International Nuclear Information System (INIS)

    Hale, Lucas M.; Lim, Hojun; Zimmerman, Jonathan A.; Battaile, Corbett C.; Weinberger, Christopher R.

    2015-01-01

    We use insights gained from atomistic simulation to develop an activation enthalpy model for dislocation slip in body-centered cubic iron. Using a classical potential that predicts dislocation core stabilities consistent with ab initio predictions, we quantify the non-Schmid stress-dependent effects of slip. The kink-pair activation enthalpy is evaluated and a model is identified as a function of the general stress state. Our model enlarges the applicability of the classic Kocks activation enthalpy model to materials with non-Schmid behavior

  17. Enthalpies of solution of ampicillin, amoxycillin and their binary mixtures at 310.15 K.

    Science.gov (United States)

    Jain, D V; Kashid, N; Kapoor, S; Chadha, R

    2000-05-15

    Enthalpies of solutions of ampicillin, amoxycillin and their binary mixtures have been determined at pH 2, 5, and 7 using C-80 calorimeter. The systems showed endothermic behaviour; molar enthalpies of solutions of ampicillin were determined to be 13.32, 15.89 and 23.21 kJ mol(-1) and amoxycillin were 16.32, 18.45 and 26. 25 kJ mol(-1) at pH 2, 5, and 7, respectively. The excess molar enthalpies of solution have also been calculated to find any interaction between these two drugs.

  18. Split-step eigenvector-following technique for exploring enthalpy landscapes at absolute zero.

    Science.gov (United States)

    Mauro, John C; Loucks, Roger J; Balakrishnan, Jitendra

    2006-03-16

    The mapping of enthalpy landscapes is complicated by the coupling of particle position and volume coordinates. To address this issue, we have developed a new split-step eigenvector-following technique for locating minima and transition points in an enthalpy landscape at absolute zero. Each iteration is split into two steps in order to independently vary system volume and relative atomic coordinates. A separate Lagrange multiplier is used for each eigendirection in order to provide maximum flexibility in determining step sizes. This technique will be useful for mapping the enthalpy landscapes of bulk systems such as supercooled liquids and glasses.

  19. Utilization of casting ladle lining enthalpy for heating gas savings in the course of ladle preheating

    OpenAIRE

    Jančar, D.; Klarova, M.; Tvardek, P.; Vlček, J.; Hašek, P.; Ovčačik, F.

    2014-01-01

    During the long-term staying of steel in ladle within the period from the tap until the end of continuous casting takes place a great amount of heat accumulates in lining. For its utilization is necessary to optimize heat operation of ladle lining. The demanded enthalpy of ladle before tap and the real enthalpy of ladle as things stand are needed for heating gas savings during the preheating. The enthalpy changes of ladle lining are in the course of their cycling in steelworks solved by the m...

  20. Global energy transports and the influence of clouds on transport requirements - A satellite analysis

    Science.gov (United States)

    Sohn, Byung-Ju; Smith, Eric A.

    1992-01-01

    This report investigates the impact of differential net radiative heating on 2D energy transports within the atmosphere ocean system and the role of clouds on this process. The 2D mean energy transports, in answer to zonal and meridional gradients in the net radiation field, show an east-west coupled dipole structure in which the Pacific acts as the major energy source and North Africa as the major energy sink. It is demonstrated that the dipole is embedded in the secondary energy transports arising mainly from the differential heating between land and oceans in the tropics in which the tropical east-west (zonal) transports are up to 30 percent of the tropical north-south (meridional) transports.

  1. CHANGES OF THE SOLAR MERIDIONAL VELOCITY PROFILE DURING CYCLE 23 EXPLAINED BY FLOWS TOWARD THE ACTIVITY BELTS

    International Nuclear Information System (INIS)

    Cameron, R. H.; Schuessler, M.

    2010-01-01

    The solar meridional flow is an important ingredient in Babcock-Leighton type models of the solar dynamo. Global variations of this flow have been suggested to explain the variations in the amplitudes and lengths of the activity cycles. Recently, cycle-related variations in the amplitude of the P 1 2 term in the Legendre decomposition of the observed meridional flow have been reported. The result is often interpreted in terms of an overall variation in the flow amplitude during the activity cycle. Using a semi-empirical model based upon the observed distribution of magnetic flux on the solar surface, we show that the reported variations of the P 1 2 term can be explained by the observed localized inflows into the active region belts. No variation of the overall meridional flow amplitude is required.

  2. Hydride phase dissolution enthalpy in neutron irradiated Zircaloy-4

    International Nuclear Information System (INIS)

    Vizcaino, Pablo; Banchik, Abraham D.

    2003-01-01

    The differential calorimetric technique has been applied to measure the dissolution enthalpy, ΔH irrad δ→α , of zirconium hydrides precipitated in structural components removed from the Argentine Atucha 1 PHWR nuclear power plant after 10.3 EFPY. An average value of ΔH irrad δ→α = 5 kJ/mol H was obtained after the first calorimetric run. That value is seven times lower than the value of ΔH δ→α = 37.7 kJ/mol H recently determined in Zircaloy-4 specimens taken from similar unirradiated structural components using the same calorimetric technique, [1]. Post-irradiation thermal treatments gradually increase that low value towards the unirradiated value with increasing annealing temperature similar to that observed for TSSd irrad . Therefore the same H atom trapping mechanism during reactor operation already proposed to explain the evolution of TSSd irrad is also valid for Q irrad δ→α . As the ratio Q/ΔH is proportional to the number N H of H atoms precipitated as hydrides, the increment of Q irrad δ→α with the thermal treatment indicates that the value of N H also grows with the annealing reaching the value corresponding to the bulk H concentration when ΔH irrad δ→α ≅ 37 kJ/mol H. That is a direct indication that the post-irradiation thermal treatment releases the H atoms from their traps increasing the number of H atoms available to precipitate at the end of each calorimetric run and/or isothermal treatment. (author)

  3. Applicability of the theory of thermodynamic similarity to predict the enthalpies of vaporization of aliphatic aldehydes

    Science.gov (United States)

    Esina, Z. N.; Korchuganova, M. R.

    2015-06-01

    The theory of thermodynamic similarity is used to predict the enthalpies of vaporization of aliphatic aldehydes. The predicted data allow us to calculate the phase diagrams of liquid-vapor equilibrium in a binary water-aliphatic aldehyde system.

  4. Building blocks for ionic liquids: Vapor pressures and vaporization enthalpies of 1-(n-alkyl)-imidazoles

    International Nuclear Information System (INIS)

    Emel'yanenko, Vladimir N.; Portnova, Svetlana V.; Verevkin, Sergey P.; Skrzypczak, Andrzej; Schubert, Thomas

    2011-01-01

    Highlights: → We measured vapor pressures of the 1-(n-alkyl)-imidazoles by transpiration method. → Variations on the alkyl chain length n were C 3 , C 5 -C 7 , and C 9 -C 10 . → Enthalpies of vaporization were derived from (p, T) dependencies. → Enthalpies of vaporization at 298.15 K were linear dependent on the chain length. - Abstract: Vapor pressures of the linear 1-(n-alkyl)-imidazoles with the alkyl chain C 3 , C 5 -C 7 , and C 9 -C 10 have been measured by the transpiration method. The molar enthalpies of vaporization Δ l g H m of these compounds were derived from the temperature dependencies of vapor pressures. A linear correlation of enthalpies of vaporization Δ l g H m (298.15 K) of the 1-(n-alkyl)-imidazoles with the chain length has been found.

  5. Short Pulsed Laser Methods for Velocimetry and Thermometry in High Enthalpy Facilities, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — A suite of laser-based diagnostics is proposed to measure velocity and temperature simultaneously using unseeded techniques in high enthalpy flows relevant to...

  6. Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

    Science.gov (United States)

    Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

    2016-01-01

    Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes. PMID:26796523

  7. What is the enthalpy of formation of pyrazine-2-carboxylic acid?

    International Nuclear Information System (INIS)

    Miranda, Margarida S.; Duarte, Darío J.R.; Liebman, Joel F.

    2016-01-01

    There are two contemporary conflicting, indeed, incompatible determinations of measurements of the enthalpies of combustion and of formation of pyrazine-2-carboxylic acid in the literature, (−2268.0 ± 0.9 and −271.2 ± 1.1 kJ · mol −1 ) and (−2211.4 ± 0.9 and −327.8 ± 1.1 kJ · mol −1 ). The current paper discusses these two sets of values and from the use of a measurement of the enthalpy of sublimation, a newly evaluated enthalpy of formation of pyrazine itself, and of the quantum chemical calculations at the G3(MP2)//B3LYP level, the former results are accepted and the derived gas phase enthalpy of formation, −(167.6 ± 3.1) kJ · mol −1 , suggested.

  8. Thermodynamic Relationship between Enthalpy of Mixing and Excess Entropy in Liquid Binary Alloys

    OpenAIRE

    Tanaka, Toshihiro; Morita, Zen-Ichiro; Gokcen, Nev A.; Iida, Takamichi

    1993-01-01

    A solution model for liquid binary alloys has been derived, based on the free volume theory considering excess volumes of the alloys. Excess entropy and excess Gibbs energy can be evaluated from the present model using values of enthalpy of mixing and excess volume. In addition, the relationship between enthalpy of mixing and excess entropy in liquid binary alloys has been interpreted based on the present model.

  9. Formation enthalpy of NiBe and Ni5Be21

    International Nuclear Information System (INIS)

    Ivanov, M.I.; Karpova, T.F.; Dalago, N.Yu.

    1981-01-01

    The method of dissolution calorimetry is used to determine standard enthalpies of NiBe and Ni 5 Be 21 formation, which are 84.8+-2.2 and (-669+-37)kJ/mol. The enthalpy values of NiBe and Ni 5 Be 21 at 331 K are shown to coincide (within the limits of errors of these values) with the values at the standard temperature of 298.15 K [ru

  10. Kinetics of enthalpy relaxation of milk protein concentrate powder upon ageing and its effect on solubility.

    Science.gov (United States)

    Haque, Enamul; Whittaker, Andrew K; Gidley, Michael J; Deeth, Hilton C; Fibrianto, Kiki; Bhandari, Bhesh R

    2012-10-01

    Kinetics of enthalpy relaxation of milk protein concentrate (MPC) powder upon short-term (up to 67 h) storage at 25 °C and aw 0.85, and long-term (up to 48 days) storage at 25 °C and a range of aw values (0-0.85) were studied by differential scanning calorimetry (DSC). The short-term study showed a rapid recovery of enthalpy for the first 48 h, followed by a slower steady increase with time. The non-exponential β parameter was calculated using the Kohlrausch-Williams-Watts function and found to be 0.39. Long-term storage showed that enthalpy relaxation depends on both storage period and water activity. The enthalpy value was much less for lower moisture content (mc) (aw ≤ 0.23, mc ≤ 5.5%) than for higher mc (aw ≥ 0.45, mc ≥ 8%) samples for a particular storage period. The results suggest that the presence of more water molecules, in close proximity to the protein surface facilitates kinetic unfreezing and subsequent motion of molecular segments of protein molecules towards thermodynamic equilibrium. Although de-ageing of stored samples did not reverse storage-induced solubility losses, the timescale of enthalpy relaxation was similar to that of solubility loss. It is suggested that enthalpy relaxation within stored samples allows structural rearrangements that are responsible for subsequent solubility decreases. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. O-H bond dissociation enthalpies in oximes: order restored.

    Science.gov (United States)

    Pratt, Derek A; Blake, Jessie A; Mulder, Peter; Walton, John C; Korth, Hans-Gert; Ingold, Keith U

    2004-09-01

    The O-H bond dissociation enthalpies (BDEs) of 13 oximes, RR'C=NOH, having R and/or R' = H, alkyl, and aryl are reported. Experimental anchor points used to validate the results of theoretical calculations include (1) the O-H BDEs of (t-Bu)2C=NOH, t-Bu(i-Pr)C=NOH, and t-Bu(1-Ad)C=NOH determined earlier from the heat released in the reaction of (t-Bu)2C=NO* with (PhNH)2 in benzene and EPR spectroscopy (Mahoney, L. R.; Mendenhall, G. D.; Ingold, K. U. J. Am. Chem. Soc. 1973, 95, 8610), all of which were decreased by 1.7 kcal/mol to reflect a revision to the heat of formation of (E)-azobenzene (which has significant ramifications for other BDEs) and to correct for the heat of hydrogen bonding of (t-Bu)2C=NOH (alphaH2 = 0.43 measured in this work) to benzene, and (2) the measured rates of thermal decomposition of six RR'C=NOCH2Ph at 423 or 443 K, which were used to derive O-H BDEs for the corresponding RR'C=NOH. Claims (Bordwell, F. G.; Ji, G. Z. J. Org. Chem. 1992, 57, 3019; Bordwell, F. G.; Zhang, S. J. Am. Chem. Soc. 1995, 117, 4858; and Bordwell, F. G.; Liu, W.-Z. J. Am. Chem. Soc. 1996, 118, 10819) that the O-H BDEs in mono- and diaryloximes are significantly lower than those for alkyloximes due to delocalization of the unpaired electron into the aromatic ring have always been inconsistent with the known structures of iminoxyl radicals as are the purported perpendicular structures, i.e., phi(Calpha-C=N-O*) = 90 degrees, for sterically hindered dialkyl iminoxyl radicals. The present results confirm the 1973 conclusion that simple steric effects, not electron delocalization or dramatic geometric changes, are responsible for the rather small differences in oxime O-H BDEs. Copyright 2004 American Chemical Society

  12. Effects of Southern Hemisphere Wind Changes on the Meridional Overturning Circulation in Ocean Models.

    Science.gov (United States)

    Gent, Peter R

    2016-01-01

    Observations show that the Southern Hemisphere zonal wind stress maximum has increased significantly over the past 30 years. Eddy-resolving ocean models show that the resulting increase in the Southern Ocean mean flow meridional overturning circulation (MOC) is partially compensated by an increase in the eddy MOC. This effect can be reproduced in the non-eddy-resolving ocean component of a climate model, providing the eddy parameterization coefficient is variable and not a constant. If the coefficient is a constant, then the Southern Ocean mean MOC change is balanced by an unrealistically large change in the Atlantic Ocean MOC. Southern Ocean eddy compensation means that Southern Hemisphere winds cannot be the dominant mechanism driving midlatitude North Atlantic MOC variability.

  13. Reduced interdecadal variability of Atlantic Meridional Overturning Circulation under global warming.

    Science.gov (United States)

    Cheng, Jun; Liu, Zhengyu; Zhang, Shaoqing; Liu, Wei; Dong, Lina; Liu, Peng; Li, Hongli

    2016-03-22

    Interdecadal variability of the Atlantic Meridional Overturning Circulation (AMOC-IV) plays an important role in climate variation and has significant societal impacts. Past climate reconstruction indicates that AMOC-IV has likely undergone significant changes. Despite some previous studies, responses of AMOC-IV to global warming remain unclear, in particular regarding its amplitude and time scale. In this study, we analyze the responses of AMOC-IV under various scenarios of future global warming in multiple models and find that AMOC-IV becomes weaker and shorter with enhanced global warming. From the present climate condition to the strongest future warming scenario, on average, the major period of AMOC-IV is shortened from ∼50 y to ∼20 y, and the amplitude is reduced by ∼60%. These reductions in period and amplitude of AMOC-IV are suggested to be associated with increased oceanic stratification under global warming and, in turn, the speedup of oceanic baroclinic Rossby waves.

  14. A reconstructed South Atlantic Meridional Overturning Circulation time series since 1870

    Science.gov (United States)

    Lopez, Hosmay; Goni, Gustavo; Dong, Shenfu

    2017-04-01

    This study reconstructs a century-long South Atlantic Meridional Overturning Circulation (SAMOC) index. The reconstruction is possible due to its covariability with sea surface temperature (SST). A singular value decomposition (SVD) method is applied to the correlation matrix of SST and SAMOC. The SVD is performed on the trained period (1993 to present) for which Expendable Bathythermographs and satellite altimetry observations are available. The joint modes obtained are used in the reconstruction of a monthly SAMOC time series from 1870 to present. The reconstructed index is highly correlated to the observational based SAMOC time series during the trained period and provides a long historical estimate. It is shown that the Interdecadal Pacific Oscillation (IPO) is the leading mode of SAMOC-SST covariability, explaining 85% with the Atlantic Niño accounting for less than 10%. The reconstruction shows that SAMOC has recently shifted to an anomalous positive period, consistent with a recent positive shift of the IPO.

  15. Reduced interdecadal variability of Atlantic Meridional Overturning Circulation under global warming

    Science.gov (United States)

    Cheng, Jun; Liu, Zhengyu; Zhang, Shaoqing; Liu, Wei; Dong, Lina; Liu, Peng; Li, Hongli

    2016-03-01

    Interdecadal variability of the Atlantic Meridional Overturning Circulation (AMOC-IV) plays an important role in climate variation and has significant societal impacts. Past climate reconstruction indicates that AMOC-IV has likely undergone significant changes. Despite some previous studies, responses of AMOC-IV to global warming remain unclear, in particular regarding its amplitude and time scale. In this study, we analyze the responses of AMOC-IV under various scenarios of future global warming in multiple models and find that AMOC-IV becomes weaker and shorter with enhanced global warming. From the present climate condition to the strongest future warming scenario, on average, the major period of AMOC-IV is shortened from ˜50 y to ˜20 y, and the amplitude is reduced by ˜60%. These reductions in period and amplitude of AMOC-IV are suggested to be associated with increased oceanic stratification under global warming and, in turn, the speedup of oceanic baroclinic Rossby waves.

  16. There is no real evidence for a diminishing trend of the Atlantic meridional overturning circulation

    Directory of Open Access Journals (Sweden)

    A. Parker

    2016-01-01

    Full Text Available The Atlantic Meridional Overturning Circulation (AMOC is part of the great ocean “conveyor belt” that circulates heat around the globe. Since the early 2000s, ocean sensors have started to monitor the AMOC, but the measurements are still far from accurate and the time window does not permit the separation of short term variability from a longer term trend. Other works have claimed that global warming is slowing down the AMOC, based on models and proxies of temperatures. Some other observations demonstrate a stable circulation of the oceans. By using tide gauge data complementing recent satellite and ocean sensor observations, the stability of the AMOC is shown to go back to 1860. It is concluded that no available information has the due accuracy and time coverage to show a clear trend outside the inter-annual and multi-decadal variability in the direction of increasing or decreasing strength over the last decades.

  17. The South American Meridional B-field Array (SAMBA) and Pc4-5 Wave Studies

    Science.gov (United States)

    Sterner, N. L.; Zesta, E.; Boudouridis, A.; Moldwin, M.; Yizengaw, E.; Chi, P. J.

    2010-12-01

    The Antarctic continent, the only landmass in the southern polar region, offers the unique opportunity for observations that geomagnetically range from polar latitudes to well into the inner magnetosphere, thus enabling conjugate observations in a wide range of geomagnetic latitudes. The SAMBA (South American Meridional B-field Array) chain is a meridional chain of 12 magnetometers, 11 of them at L=1.1 to L=2.5 along the coast of Chile and in the Antarctica peninsula, and one auroral station along the same meridian. SAMBA is conjugate to the northern hemisphere MEASURE and McMAC chains, offering unique opportunities for inter-hemispheric studies. In particular, we study asymmetries in the power of ULF waves and the role of the ionosphere in such observed asymmetries. Utilizing conjugate magnetometer stations at L=1.7 and L=2.3, we previously demonstrated that the northern hemisphere consistently shows higher ULF wave power. One possible reason for the asymmetry is solar zenith angles differences with the northern hemisphere station being closer to the ecliptic plain and having a higher power ratio. These hemispheric differences were also observed with TEC measurements indicating that the north and south conjugate ionospheres are similarly asymmetric. The initial study was done with Pc3 waves, which include the resonance frequencies for the flux tubes of our conjugate stations. We now extend the study to Pc4 and Pc5 waves that reach the lower latitudes via different mechanisms and compare these waves to the resonant Pc3 waves.

  18. Does δ18O of O2 record meridional shifts in tropical rainfall?

    Directory of Open Access Journals (Sweden)

    A. M. Seltzer

    2017-10-01

    Full Text Available Marine sediments, speleothems, paleo-lake elevations, and ice core methane and δ18O of O2 (δ18Oatm records provide ample evidence for repeated abrupt meridional shifts in tropical rainfall belts throughout the last glacial cycle. To improve understanding of the impact of abrupt events on the global terrestrial biosphere, we present composite records of δ18Oatm and inferred changes in fractionation by the global terrestrial biosphere (ΔεLAND from discrete gas measurements in the WAIS Divide (WD and Siple Dome (SD Antarctic ice cores. On the common WD timescale, it is evident that maxima in ΔεLAND are synchronous with or shortly follow small-amplitude WD CH4 peaks that occur within Heinrich stadials 1, 2, 4, and 5 – periods of low atmospheric CH4 concentrations. These local CH4 maxima have been suggested as markers of abrupt climate responses to Heinrich events. Based on our analysis of the modern seasonal cycle of gross primary productivity (GPP-weighted δ18O of terrestrial precipitation (the source water for atmospheric O2 production, we propose a simple mechanism by which ΔεLAND tracks the centroid latitude of terrestrial oxygen production. As intense rainfall and oxygen production migrate northward, ΔεLAND should decrease due to the underlying meridional gradient in rainfall δ18O. A southward shift should increase ΔεLAND. Monsoon intensity also influences δ18O of precipitation, and although we cannot determine the relative contributions of the two mechanisms, both act in the same direction. Therefore, we suggest that abrupt increases in ΔεLAND unambiguously imply a southward shift of tropical rainfall. The exact magnitude of this shift, however, remains under-constrained by ΔεLAND.

  19. Does δ18O of O2 record meridional shifts in tropical rainfall?

    Science.gov (United States)

    Seltzer, Alan M.; Buizert, Christo; Baggenstos, Daniel; Brook, Edward J.; Ahn, Jinho; Yang, Ji-Woong; Severinghaus, Jeffrey P.

    2017-10-01

    Marine sediments, speleothems, paleo-lake elevations, and ice core methane and δ18O of O2 (δ18Oatm) records provide ample evidence for repeated abrupt meridional shifts in tropical rainfall belts throughout the last glacial cycle. To improve understanding of the impact of abrupt events on the global terrestrial biosphere, we present composite records of δ18Oatm and inferred changes in fractionation by the global terrestrial biosphere (ΔɛLAND) from discrete gas measurements in the WAIS Divide (WD) and Siple Dome (SD) Antarctic ice cores. On the common WD timescale, it is evident that maxima in ΔɛLAND are synchronous with or shortly follow small-amplitude WD CH4 peaks that occur within Heinrich stadials 1, 2, 4, and 5 - periods of low atmospheric CH4 concentrations. These local CH4 maxima have been suggested as markers of abrupt climate responses to Heinrich events. Based on our analysis of the modern seasonal cycle of gross primary productivity (GPP)-weighted δ18O of terrestrial precipitation (the source water for atmospheric O2 production), we propose a simple mechanism by which ΔɛLAND tracks the centroid latitude of terrestrial oxygen production. As intense rainfall and oxygen production migrate northward, ΔɛLAND should decrease due to the underlying meridional gradient in rainfall δ18O. A southward shift should increase ΔɛLAND. Monsoon intensity also influences δ18O of precipitation, and although we cannot determine the relative contributions of the two mechanisms, both act in the same direction. Therefore, we suggest that abrupt increases in ΔɛLAND unambiguously imply a southward shift of tropical rainfall. The exact magnitude of this shift, however, remains under-constrained by ΔɛLAND.

  20. Asymmetric response of the Atlantic Meridional Ocean Circulation to freshwater anomalies in a strongly-eddying global ocean model

    NARCIS (Netherlands)

    Brunnabend, Sandra Esther|info:eu-repo/dai/nl/371740878; Dijkstra, Henk A.|info:eu-repo/dai/nl/073504467

    2017-01-01

    The Atlantic Meridional Overturning Circulation (AMOC) responds sensitively to density changes in regions of deepwater formation. In this paper, we investigate the nonlinear response of the AMOC to large amplitude freshwater changes around Greenland using a strongly-eddying global ocean model. Due

  1. Enthalpy of cooperative hydrogen bonding in complexes of tertiary amines with aliphatic alcohols: Calorimetric study

    International Nuclear Information System (INIS)

    Zaitseva, Ksenia V.; Varfolomeev, Mikhail A.; Novikov, Vladimir B.; Solomonov, Boris N.

    2011-01-01

    Research highlights: → Solution enthalpies of aliphatic alcohols in tertiary amines and vice versa were measured. → The enthalpies of specific interaction of amines in aliphatic alcohols are lower than the enthalpies of hydrogen bonding in 1:1 complexes amine-alcohol determined in base media. → Hydrogen bond cooperativity factors in multi-particle complexes of alcohols with aromatic amines are approximately equal for all alcohols. → Hydrogen bond cooperativity factors in multi-particle complexes of alcohols with trialkylamines decrease with increasing of alkyl radical length in alcohol and amine molecules. - Abstract: The work is devoted to the investigation of thermodynamics of specific interaction of the tertiary aliphatic and aromatic amines with associated solvents as which aliphatic alcohols were taken. Solution enthalpies of aliphatic alcohols in amines (tri-n-propylamine, 2-methylpyridine, 3-methylpyridine, N-methylimidazole) as well as amines in alcohols were measured at infinite dilution. The enthalpies of specific interaction (H-bonding) in systems studied were determined based on experimental data. The enthalpies of specific interaction of amines in aliphatic alcohols significantly lower than the enthalpies of hydrogen bonding in complexes amine-alcohol of 1:1 composition determined in base media due to the reorganization of aliphatic alcohols as solvents. The determination of solvent reorganization contribution makes possible to define the hydrogen bonding enthalpies of amines with clusters of alcohols. Obtained enthalpies of hydrogen bonding in multi-particle complexes are sensitive to the influence of cooperative effect. It was shown, that hydrogen bond cooperativity factors in multi-particle complexes of alcohols with amines are approximately equal for all alcohols when pyridines and N-methylimidazole as solutes are used. At the same time, H-bonding cooperativity factors in complexes of trialkylamines with associative species of alcohols

  2. Molar heat capacity and molar excess enthalpy measurements in aqueous amine solutions

    Science.gov (United States)

    Poozesh, Saeed

    Experimental measurements of molar heat capacity and molar excess enthalpy for 1, 4-dimethyl piperazine (1, 4-DMPZ), 1-(2-hydroxyethyl) piperazine (1, 2-HEPZ), I-methyl piperazine (1-MPZ), 3-morpholinopropyl amine (3-MOPA), and 4-(2-hydroxy ethyl) morpholine (4, 2-HEMO) aqueous solutions were carried out in a C80 heat flow calorimeter over a range of temperatures from (298.15 to 353.15) K and for the entire range of the mole fractions. The estimated uncertainty in the measured values of the molar heat capacity and molar excess enthalpy was found to be +/- 2%. Among the five amines studied, 3-MOPA had the highest values of the molar heat capacity and 1-MPZ the lowest. Values of molar heat capacities of amines were dominated by --CH 2, --N, --OH, --O, --NH2 groups and increased with increasing temperature, and contributions of --NH and --CH 3 groups decreased with increasing temperature for these cyclic amines. Molar excess heat capacities were calculated from the measured molar heat capacities and were correlated as a function of the mole fractions employing the Redlich-Kister equation. The molar excess enthalpy values were also correlated as a function of the mole fractions employing the Redlich-Kister equation. Molar enthalpies at infinite dilution were derived. Molar excess enthalpy values were modeled using the solution theory models: NRTL (Non Random Two Liquid) and UNIQUAC (UNIversal QUAsi Chemical) and the modified UNIFAC (UNIversal quasi chemical Functional group Activity Coefficients - Dortmund). The modified UNIFAC was found to be the most accurate and reliable model for the representation and prediction of the molar excess enthalpy values. Among the five amines, the 1-MPZ + water system exhibited the highest values of molar excess enthalpy on the negative side. This study confirmed the conclusion made by Maham et al. (71) that -CH3 group contributed to higher molar excess enthalpies. The negative excess enthalpies were reduced due to the contribution of

  3. Enthalpies of sublimation of ferrocene and nickelocene measured by calorimetry and the method of Langmuir

    Energy Technology Data Exchange (ETDEWEB)

    Rojas, Aaron, E-mail: arojas@cinvestav.mx [Departamento de Quimica del Centro de Investigacion y de Estudios Avanzados del IPN, Av. Instituto Politecnico Nacional 2508, C.P. 07360, Mexico D.F. (Mexico); Vieyra-Eusebio, Maria Teresa [Departamento de Quimica del Centro de Investigacion y de Estudios Avanzados del IPN, Av. Instituto Politecnico Nacional 2508, C.P. 07360, Mexico D.F. (Mexico)

    2011-11-15

    Highlights: > Calorimetric enthalpies of sublimation of ferrocene and nickelocene are supplied. > Sublimation enthalpies of both metallocenes were also obtained by indirect Langmuir's method. > Calorimetric and indirect enthalpies of sublimation are comparable in accuracy and dispersion. > Sublimation enthalpies are congruent with both compounds being monoclinic and isostructural. - Abstract: A quick and accurate methodology that is based on Langmuir's equation and that is developed by utilising a DSC7 device is proposed for the measurement of the enthalpies of sublimation of substances characterised by vapour pressures of approximately 1.0 Pa at room temperature. The procedure was applied to ferrocene and nickelocene; the accuracy and uncertainty associated with the experimental results show that the reliability of the developed indirect method is comparable to the direct calorimetric measurements also performed in this work. Furthermore, the melting data and crystal-phase heat capacities for both metallocenes were calorimetrically measured, whereas the gas-phase heat capacity for each metallic bis(cyclopentadienyl) was theoretically estimated by DFT calculations.

  4. Chemical and thermochemical aspects of the ozonolysis of ethyl oleate: decomposition enthalpy of ethyl oleate ozonide.

    Science.gov (United States)

    Cataldo, Franco

    2013-01-01

    Neat ethyl oleate was ozonized in a bubble reactor and the progress of the ozonolysis was followed by infrared (FT-IR) spectroscopy and by the differential scanning calorimetry (DSC). The ozonolysis was conducted till a molar ratio O3/C=C≈1 when the exothermal reaction spontaneously went to completion. A specific thermochemical calculation on ethyl oleate ozonation has been made to determine the theoretical heat of the ozonization reaction using the group increment approach. A linear relationship was found both in the integrated absorptivity of the ozonide infrared band at 1110 cm(-1) and the ozonolysis time as well as the thermal decomposition enthalpy of the ozonides and peroxides formed as a result of the ozonation. The DSC decomposition temperature of ozonated ethyl oleate occurs with an exothermal peak at about 150-155 °C with a decomposition enthalpy of 243.0 kJ/mol at molar ratio O3/C=C≈1. It is shown that the decomposition enthalpy of ozonized ethyl oleate is a constant value (≈243 kJ/mol) at any stage of the O3/C=C once an adequate normalization of the decomposition enthalpy for the amount of the adsorbed ozone is taken into consideration. The decomposition enthalpy of ozonized ethyl oleate was also calculated using a simplified thermochemical model, obtaining a result in reasonable agreement with the experimental value. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  5. Development of equations for differential and integral enthalpy change of adsorption for simulation studies.

    Science.gov (United States)

    Do, D D; Nicholson, D; Fan, Chunyan

    2011-12-06

    We present equations to calculate the differential and integral enthalpy changes of adsorption for their use in Monte Carlo simulation. Adsorption of a system of N molecules, subject to an external potential energy, is viewed as one of transferring these molecules from a reference gas phase (state 1) to the adsorption system (state 2) at the same temperature and equilibrium pressure (same chemical potential). The excess amount adsorbed is the difference between N and the hypothetical amount of gas occupying the accessible volume of the system at the same density as the reference gas. The enthalpy change is a state function, which is defined as the difference between the enthalpies of state 2 and state 1, and the isosteric heat is defined as the negative of the derivative of this enthalpy change with respect to the excess amount of adsorption. It is suitable to determine how the system behaves for a differential increment in the excess phase adsorbed under subcritical conditions. For supercritical conditions, use of the integral enthalpy of adsorption per particle is recommended since the isosteric heat becomes infinite at the maximum excess concentration. With these unambiguous definitions we derive equations which are applicable for a general case of adsorption and demonstrate how they can be used in a Monte Carlo simulation. We apply the new equations to argon adsorption at various temperatures on a graphite surface to illustrate the need to use the correct equation to describe isosteric heat of adsorption. © 2011 American Chemical Society

  6. Enthalpy relaxation studies of two structurally related amorphous drugs and their binary dispersions.

    Science.gov (United States)

    Bansal, Shyam Sunder; Kaushal, Aditya Mohan; Bansal, Arvind Kumar

    2010-11-01

    The purpose of the current study was to evaluate the enthalpy relaxation behavior of valdecoxib (VLB) and etoricoxib (ETB) and their binary dispersions to derive relaxation constants and to understand their molecular mobilities. Solid dispersions of VLB and ETB were prepared with 1%, 2%, 5%, 10%, 15%, and 20% (w/w) concentrations of polyvinylpyrrolidone (PVP) in situ using differential scanning calorimetry (DSC). Enthalpy relaxation studies were carried out with isothermal storage periods of 1, 2, 4, 6, 16, and 24 hours at 40°C and 0% relative humidity (RH). PVP increased the glass transition temperature (T(g)) and decreased the enthalpy relaxation. Significant differences between two drugs were observed with respect to their relaxation behavior which may be due to differences in intermolecular interactions as predicted by Couchman-Karasz equation and molecular mobility. Kohlrausch-Williams-Watts equation was found to be inadequate in describing complex molecular relaxations in binary dispersions. The enthalpy relaxation behavior of VLB and ETB was found to be significantly different. PVP stabilized VLB significantly; however, its effect on ETB was negligible. The extent of enthalpy relaxation was found to correlate with hydrogen bonding tendency of the drug molecules. The outcome can help in rational designing of amorphous systems with optimal performance.

  7. Enthalpies of sublimation of ferrocene and nickelocene measured by calorimetry and the method of Langmuir

    International Nuclear Information System (INIS)

    Rojas, Aaron; Vieyra-Eusebio, Maria Teresa

    2011-01-01

    Highlights: → Calorimetric enthalpies of sublimation of ferrocene and nickelocene are supplied. → Sublimation enthalpies of both metallocenes were also obtained by indirect Langmuir's method. → Calorimetric and indirect enthalpies of sublimation are comparable in accuracy and dispersion. → Sublimation enthalpies are congruent with both compounds being monoclinic and isostructural. - Abstract: A quick and accurate methodology that is based on Langmuir's equation and that is developed by utilising a DSC7 device is proposed for the measurement of the enthalpies of sublimation of substances characterised by vapour pressures of approximately 1.0 Pa at room temperature. The procedure was applied to ferrocene and nickelocene; the accuracy and uncertainty associated with the experimental results show that the reliability of the developed indirect method is comparable to the direct calorimetric measurements also performed in this work. Furthermore, the melting data and crystal-phase heat capacities for both metallocenes were calorimetrically measured, whereas the gas-phase heat capacity for each metallic bis(cyclopentadienyl) was theoretically estimated by DFT calculations.

  8. Glacial climate sensitivity to different states of the Atlantic Meridional Overturning Circulation: results from the IPSL model

    Directory of Open Access Journals (Sweden)

    M. Kageyama

    2009-09-01

    Full Text Available Paleorecords from distant locations on the globe show rapid and large amplitude climate variations during the last glacial period. Here we study the global climatic response to different states of the Atlantic Meridional Overturning Circulation (AMOC as a potential explanation for these climate variations and their possible connections. We analyse three glacial simulations obtained with an atmosphere-ocean coupled general circulation model and characterised by different AMOC strengths (18, 15 and 2 Sv resulting from successive ~0.1 Sv freshwater perturbations in the North Atlantic. These AMOC states suggest the existence of a freshwater threshold for which the AMOC collapses. A weak (18 to 15 Sv AMOC decrease results in a North Atlantic and European cooling. This cooling is not homogeneous, with even a slight warming over the Norwegian Sea. Convection in this area is active in both experiments, but surprisingly stronger in the 15 Sv simulation, which appears to be related to interactions with the atmospheric circulation and sea-ice cover. Far from the North Atlantic, the climatic response is not significant. The climate differences for an AMOC collapse (15 to 2 Sv are much larger and of global extent. The timing of the climate response to this AMOC collapse suggests teleconnection mechanisms. Our analyses focus on the North Atlantic and surrounding regions, the tropical Atlantic and the Indian monsoon region. The North Atlantic cooling associated with the AMOC collapse induces a cyclonic atmospheric circulation anomaly centred over this region, which modulates the eastward advection of cold air over the Eurasian continent. This can explain why the cooling is not as strong over western Europe as over the North Atlantic. In the Tropics, the southward shift of the Inter-Tropical Convergence Zone appears to be strongest over the Atlantic and Eastern Pacific and results from an adjustment of the atmospheric and oceanic heat transports. Finally, the

  9. High Resolution Model Development to Quantify the Impact of Icebergs on the Stability of the Atlantic Meridional Overturning Circulation

    Energy Technology Data Exchange (ETDEWEB)

    Condron, Alan [Univ. of Massachusetts, Amherst, MA (United States)

    2016-10-18

    In the present-day North Atlantic Ocean, relatively warm and salty water moves northwards from the tropics to the high latitudes, sinks, and returns southward towards the equator as North Atlantic Deep Water, forming the so called Atlantic Meridional Overturning Circulation (AMOC). It has been found that the stability of the AMOC is non-linearly related to the freshwater budget of the North Atlantic. In this way, additional fresh water can be added to the ocean with little impact, until a tipping point is reached that causes the AMOC to suddenly weaken and the Northern Hemisphere to abruptly cool. A great deal of uncertainty still remains over the sensitivity of the AMOC to changes in freshwater discharge as a result of the unrealistic manner in which freshwater has historically been added to climate models. Frequently, freshwater is discharged in ocean models entirely as liquid water, but in reality a large fraction of freshwater entering the ocean is ice calving from marine glaciers (half for Antarctica and two-thirds for Greenland). To more accurately quantify AMOC sensitivity to past and future changes in freshwater input, this project developed a comprehensive iceberg model to more realistically simulate the interaction between the cryosphere and the oceans at high-latitudes. The iceberg model created is written in Fortran90 and designed to scale efficiently on High Performance Computing (HPC) clusters so that tens-of-thousands of icebergs can be simulated at any time. Experiments performed with our model showed that in the Pleistocene there would have been enormous floods of freshwater released into the North Atlantic that would have transported icebergs and meltwater along the entire east coast of the United States, as far south as Florida Keys. In addition, high-resolution, modern-day, model simulations showed that if the Greenland Ice Sheet continues to melt at its current rate then there will be a 6-fold increase in the number of icebergs drifting in the

  10. Hosed vs. unhosed: interruptions of the Atlantic Meridional Overturning Circulation in a global coupled model, with and without freshwater forcing

    Science.gov (United States)

    Brown, Nicolas; Galbraith, Eric D.

    2016-08-01

    It is well known that glacial periods were punctuated by abrupt climate changes, with large impacts on air temperature, precipitation, and ocean circulation across the globe. However, the long-held idea that freshwater forcing, caused by massive iceberg discharges, was the driving force behind these changes has been questioned in recent years. This throws into doubt the abundant literature on modelling abrupt climate change through "hosing" experiments, whereby the Atlantic Meridional Overturning Circulation (AMOC) is interrupted by an injection of freshwater to the North Atlantic: if some, or all, abrupt climate change was not driven by freshwater input, could its character have been very different than the typical hosed experiments? Here, we describe spontaneous, unhosed oscillations in AMOC strength that occur in a global coupled ocean-atmosphere model when integrated under a particular background climate state. We compare these unhosed oscillations to hosed oscillations under a range of background climate states in order to examine how the global imprint of AMOC variations depends on whether or not they result from external freshwater input. Our comparison includes surface air temperature, precipitation, dissolved oxygen concentrations in the intermediate-depth ocean, and marine export production. The results show that the background climate state has a significant impact on the character of the freshwater-forced AMOC interruptions in this model, with particularly marked variations in tropical precipitation and in the North Pacific circulation. Despite these differences, the first-order patterns of response to AMOC interruptions are quite consistent among all simulations, implying that the ocean-sea ice-atmosphere dynamics associated with an AMOC weakening dominate the global response, regardless of whether or not freshwater input is the cause. Nonetheless, freshwater addition leads to a more complete shutdown of the AMOC than occurs in the unhosed oscillations

  11. Enthalpies of solution of methylcalix[4]resorcinarene in non-aqueous solvents as a function of concentration and temperature

    Energy Technology Data Exchange (ETDEWEB)

    Riveros, Diana C. [Laboratorio de Termodinamica de Soluciones, Departamento de Quimica, Facultad de Ciencias, Universidad de los Andes, Bogota D.C. (Colombia); Martinez, Fleming [Grupo de Investigaciones Farmaceutico-Fisicoquimicas, Departamento de Farmacia, Facultad de Ciencias, Universidad Nacional de Colombia, Bogota D.C. (Colombia); Vargas, Edgar F., E-mail: edvargas@uniandes.edu.co [Laboratorio de Termodinamica de Soluciones, Departamento de Quimica, Facultad de Ciencias, Universidad de los Andes, Bogota D.C. (Colombia)

    2012-11-20

    Highlights: Black-Right-Pointing-Pointer The solution enthalpies of methylcalix[4]resorcinarene in alcohols have been measured. Black-Right-Pointing-Pointer The solution enthalpies of methylcalix[4]resorcinarene in alcohols are endothermic. Black-Right-Pointing-Pointer Enthalpies of transference are interpreted in terms of proton donor capacity of alcohols. - Abstract: Enthalpies of solution of 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octahydroxyresorci[4]arene in methanol, ethanol and propanol as a function of molal concentration at (288.15, 298.15 and 308.15) K were measured calorimetrically. The enthalpies of solvation were estimated. Using propanol as the referent solvent, transfer properties to other alcohols were also calculated. In addition, temperature dependence of the enthalpy of solution at infinite dilution was also obtained. The data were interpreted in terms of solute-solvent interactions.

  12. Enthalpies of solution of methylcalix[4]resorcinarene in non-aqueous solvents as a function of concentration and temperature

    International Nuclear Information System (INIS)

    Riveros, Diana C.; Martínez, Fleming; Vargas, Edgar F.

    2012-01-01

    Highlights: ► The solution enthalpies of methylcalix[4]resorcinarene in alcohols have been measured. ► The solution enthalpies of methylcalix[4]resorcinarene in alcohols are endothermic. ► Enthalpies of transference are interpreted in terms of proton donor capacity of alcohols. - Abstract: Enthalpies of solution of 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octahydroxyresorci[4]arene in methanol, ethanol and propanol as a function of molal concentration at (288.15, 298.15 and 308.15) K were measured calorimetrically. The enthalpies of solvation were estimated. Using propanol as the referent solvent, transfer properties to other alcohols were also calculated. In addition, temperature dependence of the enthalpy of solution at infinite dilution was also obtained. The data were interpreted in terms of solute–solvent interactions.

  13. The South American Meridional B-field Array (SAMBA) and opportunities for inter- hemispheric studies

    Science.gov (United States)

    Zesta, E.; Boudouridis, A.; Moldwin, M. B.; Weygand, J. M.; Chi, P. J.

    2009-05-01

    The Antarctic continent, the only landmass in the southern polar region, offers the unique opportunity for observations that geomagnetically range from polar latitudes to well into the inner magnetosphere, thus enabling conjugate observations in a wide range of geomagnetic latitudes. The SAMBA (South American Meridional B-field Array) chain is a meridional chain of 12 magnetometers, 11 of them at L=1.1 to L=2.5 along the coast of Chile and in the Antarctica peninsula, and one auroral station along the same meridian. SAMBA is ideal for low and mid-latitude studies of geophysical events and ULF waves. It is conjugate to the northern hemisphere MEASURE and McMAC chains, offering unique opportunities for inter-hemispheric studies. We use 5 of the SAMBA stations and a number of conjugate stations from the Northern hemisphere to determine the field line resonance (FLR) frequency of closely spaced flux tubes in the inner magnetosphere. Standard inversion techniques are used to derive the equatorial mass density of these flux tubes from the FLRs. From our conjugate pairs we find, surprisingly, that the derived mass density of closely spaced flux tubes, from L=1.6 to L=2.5, drops at a rate that cannot be predicted by any of the existing models or agree with past observations. We also study asymmetries in the power of Pc3 waves. We find that during northern summer solstice the waves are significantly stronger at the northern conjugate point, while during northern winter solstice the wave power is comparable over both conjugate points. Finally, using the SAMBA auroral station, WSD, along with all available southern auroral stations we calculate a southern AE index and its direct conjugate northern AE index and compare both with the standard AE index. We explore under what conditions the north-south asymmetries in the AE calculation are due to the significant gap of auroral stations in the Southern hemisphere and under what conditions the asymmetries have a geophysical source.

  14. Impact of the Indonesian Throughflow on the Atlantic Meridional Overturning Circulation

    Science.gov (United States)

    Le Bars, Dewi; Dijkstra, Henk

    2014-05-01

    Understanding the mechanisms controlling the strength and variability of the Atlantic Meridional Overturning Circulation (AMOC) is one of the main topics of climate science and in particular physical oceanography. Current simple representations of the global ocean overturning separates the surface return flow to the Atlantic basin into a cold water path through the Drake Passage and a warm water path through the Indonesian Throughflow and Agulhas leakage. The relative importance of these two paths has been investigated in non-eddying ocean models. In these models the Agulhas retroflection cannot be modelled properly, which leads to an important overestimation of the Agulhas leakage. Furthermore, it seems that the in these models the relation between the meridional density gradient and the overturning strength is greatly simplified and changes significantly when eddies are resolved (Den Toom et al. 2013). As a result, the impact of the Pacific-Indian Oceans exchange through the Indonesian Throughflow on the AMOC is still unknown. To investigate this question we run a state-of-the-art ocean model, the Parallel Ocean Program (POP), globally, at eddy resolving resolution (0.1º). Using climatological forcing from the CORE dataset we perform two simulations of 110 years, a control experiment with realistic coastlines and one in which the Indonesian Passages are closed. Results show that, for a closed Indonesian Throughflow, the Indian Ocean cools down but its salinity increases. The Agulhas leakage reduces also by 3Sv (Le Bars et al. 2013) and the net effect on the south Atlantic is a cooling down and decrease salinity. The anomalies propagate slowly northward and a significant decrease of the AMOC is found at 26ºN after 50 years. This decrease AMOC also leads to reduced northward heat flux in the Atlantic. These processes are investigated with a detailed analysis of the heat and freshwater balances in the Atlantic-Arctic region and in the region south of 34ºS where

  15. Computational Investigation of Enthalpy-Entropy Compensation in Complexation of Glycoconjugated Bile Salts with β-Cyclodextrin and Analogs

    DEFF Research Database (Denmark)

    Tidemand, Kasper Damgaard; Schonbeck, Christian; Holm, Rene

    2014-01-01

    in complexation entropy with DS was not able to compensate for this unfavorable change in enthalpy induced by the HP substituents, resulting in a destabilizing effect. This was found to originate from fixation of the HP substituents and decreased free rotation of the bile salts within the CD cavities....... of water molecules in the cavity increased with the DS. Release of water from the cavity resulted in a positive enthalpy change, which correlates qualitatively with the experimentally determined increase in complexation enthalpy and contributes to the enthalpy-entropy compensation. The positive change...

  16. Enthalpies of Formation of Transition Metal Diborides: A First Principles Study

    Directory of Open Access Journals (Sweden)

    Catherine Colinet

    2015-11-01

    Full Text Available The enthalpies of formation of transition metals diborides in various structures have been obtained from density functional theory (DFT calculations in order to determine the ground state at T = 0 K and p = 0. The evolution of the enthalpies of formation along the 3D, 4D, and 5D series has been correlated to the considered crystal structures. In the whole, the calculated values of the enthalpies of formation of the diborides in their ground state are in good agreement with the experimental ones when available. The calculated values of the lattice parameters at T = 0 K of the ground state agree well with the experimental values. The total and partial electronic densities of states have been computed. Special features of the transition metal electronic partial density of states have been evidenced and correlated to the local environment of the atoms.

  17. Comparison of the enthalpy recovery and free volume of polyvinylpyrrolidone during anomalous glassy to rubbery transition.

    Science.gov (United States)

    Zelkó, Romána; Süvegh, Károly

    2004-03-01

    Previous studies confirmed that along with the structural changes of the amorphous binder, that of the polyvinylpyrrolidone, the tensile strength and consequently, the dissolution behaviour of its tablets changed significantly during the storage period. Structural formation during the glassy to rubbery transition of polyvinylpyrrolidone was followed by the changes in the free volume and enthalpy recovery values of the polymer. The results suggest that the apparent structure formation of water and polymer under glassy to rubbery transition is interrelated in a dynamic and complex manner which can be tracked by the combination of enthalpy recovery studies and positron lifetime measurements. Positron lifetime measurements more sensitively react to the structural rearrangements than enthalpy recovery, thus it can be recommended as a sensitive tool for stability tests during the formulation phase of drug development.

  18. Crystal structures of highly simplified BPTIs provide insights into hydration-driven increase of unfolding enthalpy.

    Science.gov (United States)

    Islam, Mohammad Monirul; Yohda, Masafumi; Kidokoro, Shun-Ichi; Kuroda, Yutaka

    2017-03-07

    We report a thermodynamic and structural analysis of six extensively simplified bovine pancreatic trypsin inhibitor (BPTI) variants containing 19-24 alanines out of 58 residues. Differential scanning calorimetry indicated a two-state thermal unfolding, typical of a native protein with densely packed interior. Surprisingly, increasing the number of alanines induced enthalpy stabilization, which was however over-compensated by entropy destabilization. X-ray crystallography indicated that the alanine substitutions caused the recruitment of novel water molecules facilitating the formation of protein-water hydrogen bonds and improving the hydration shells around the alanine's methyl groups, both of which presumably contributed to enthalpy stabilization. There was a strong correlation between the number of water molecules and the thermodynamic parameters. Overall, our results demonstrate that, in contrast to our initial expectation, a protein sequence in which over 40% of the residues are alanines can retain a densely packed structure and undergo thermal denaturation with a large enthalpy change, mainly contributed by hydration.

  19. Estimation of Solvation Entropy and Enthalpy via Analysis of Water Oxygen-Hydrogen Correlations.

    Science.gov (United States)

    Velez-Vega, Camilo; McKay, Daniel J J; Kurtzman, Tom; Aravamuthan, Vibhas; Pearlstein, Robert A; Duca, José S

    2015-11-10

    A statistical-mechanical framework for estimation of solvation entropies and enthalpies is proposed, which is based on the analysis of water as a mixture of correlated water oxygens and water hydrogens. Entropic contributions of increasing order are cast in terms of a Mutual Information Expansion that is evaluated to pairwise interactions. In turn, the enthalpy is computed directly from a distance-based hydrogen bonding energy algorithm. The resulting expressions are employed for grid-based analyses of Molecular Dynamics simulations. In this first assessment of the methodology, we obtained global estimates of the excess entropy and enthalpy of water that are in good agreement with experiment and examined the method's ability to enable detailed elucidation of solvation thermodynamic structures, which can provide valuable knowledge toward molecular design.

  20. Enthalpy-Based Screening of Focused Combinatorial Libraries for the Identification of Potent and Selective Ligands.

    Science.gov (United States)

    Baggio, Carlo; Udompholkul, Parima; Barile, Elisa; Pellecchia, Maurizio

    2017-12-15

    In modern drug discovery, the ability of biophysical methods, including nuclear magnetic resonance spectroscopy or surface plasmon resonance, to detect and characterize ligand-protein interactions accurately and unambiguously makes these approaches preferred versus conventional biochemical high-throughput screening of large collections of compounds. Nonetheless, ligand screening strategies that address simultaneously potency and selectivity have not yet been fully developed. In this work, we propose a novel method for screening large collections of combinatorial libraries using enthalpy measurements as a primary screening technique. We demonstrate that selecting binders that are driven by enthalpy (ΔH) results in agents that are not only potent but also more selective for a given target. This general and novel approach, we termed ΔH screening of fPOS (enthalpy screening of focused positional scanning library), combines the principles of focused combinatorial chemistry with rapid calorimetry measurements to efficiently identify potent and selective inhibitors.

  1. Do Enthalpy and Entropy Distinguish First in Class From Best in Class?

    Science.gov (United States)

    Freire, Ernesto

    2008-01-01

    A drug molecule should bind to its target with high affinity and selectivity. Since the binding affinity is a combined function of the binding enthalpy and the binding entropy, extremely high affinity requires that both terms contribute favorably to binding. The binding enthalpy, however, is notoriously more difficult to optimize than the binding entropy, a fact that has resulted in thermodynamically-unbalanced molecules that do not achieve optimal potency. In fact, with current technologies, the enthalpic optimization of drug candidates may take years and only appear in second-generation products. Within that context, it is not surprising that structure/activity relationships (SAR) that explicitly incorporate the interplay between enthalpy and entropy and accelerate the optimization process are being developed and gaining popularity. PMID:18703160

  2. Utilization of casting ladle lining enthalpy for heating gas savings in the course of ladle preheating

    Directory of Open Access Journals (Sweden)

    D. Jančar

    2014-04-01

    Full Text Available During the long-term staying of steel in ladle within the period from the tap until the end of continuous casting takes place a great amount of heat accumulates in lining. For its utilization is necessary to optimize heat operation of ladle lining. The demanded enthalpy of ladle before tap and the real enthalpy of ladle as things stand are needed for heating gas savings during the preheating. The enthalpy changes of ladle lining are in the course of their cycling in steelworks solved by the model of lining thermal state. For that purpose were conducted the operation measurements to find out the ladle lining thermal field within the whole technological flow.

  3. The enthalpies of formation of neutral and charged components of saturated vapor over europium dichloride

    International Nuclear Information System (INIS)

    Pogrebnoj, A.M.; Kudin, L.S.

    2003-01-01

    Composition of saturated vapor over europium dichloride was studied by the method of high-temperature mass spectrometry in the temperature range of 1154 - 1267 K. For neutral components of the vapor, represented by monomer and dimer molecules, partial pressures were determined. Enthalpies of sublimation of europium dichloride Δ s H 0 (298 K) as monomers (338 ± 9) and dimers (407 ± 20 kJ/mol) were calculated. Equilibrium constants of ion-molecular and ion-ionic reactions were measured, their enthalpies being ascertained. Enthalpies of formation of molecules and ions Δ f H 0 (298 K) were calculated: -486 ± 11 (EuCl 2 ), -1242 ± 22 (Eu 2 Cl 4 ), 1 ± 12 (Eu 2 Cl 2 + ), -347 ± 20 (Eu 2 Cl 3 + ), -1111 ± 42 (Eu 3 Cl 5 + ), -975 ± 20 (EuCl 3 - ), -1309 ± 17(EuCl 4 - ), -1734 ± 20 (Eu 2 Cl 5 - ) kJ/mol [ru

  4. Standard enthalpy of formation of Sm6UO12 acid dissolution calorimetry

    International Nuclear Information System (INIS)

    Venkata Krishnan, R.; Jogeswararao, G.; Ananthasivan, K.

    2016-01-01

    The standard molar enthalpies of formation of Δ f (298 K) of Sm 6 UO 12 have been determined by using an indigenously developed isoperibol acid solution calorimeter. The water equivalent of this calorimeter was determined by electrical calibration. The accuracy of measurement were determined by using standard materials KCl and tris(hydroxyl methyl) amino-methane (TRIS) and was found to be within ±2%. The enthalpies of solution at 298 K of Sm 2 O 3 , UO 3 and Sm 6 UO 12 were measured by using this calorimeter. From these experimental results the enthalpies of formation of Sm 6 UO 12 at 298 K were computed by using Hess's law of summation. (author)

  5. Structure of metal β-diketonates and their enthalpies of vaporization

    International Nuclear Information System (INIS)

    Domrachev, G.A.; Sevast'yanov, V.G.; Zakharov, L.N.; Krasnodubskaya, S.V.; AN SSSR, Moscow. Inst. Obshchej i Neorganicheskoj Khimii)

    1987-01-01

    Using the method of additive schemes in combinaion with the structural estimation of the degree of screening of the central atom and other elements of β-diketonate molecule while analyzing the experimental enthalpies of vaporization, the contributions of separate fragments of complexes into the enthalpy of vaporization are found. It is shown that energies of intermolecular interaction in a condensed phase of monomeric metal β-diketonates with identical substituents do not depend on the central atom type. The enthalpies of dimer dissociation in a series of rare earth dipivaloylmethanates calculated. The proposed approach is advisable fo selecting forms of metal β-diketonates, the most suitable for the purposes of deep purificaion, which are characterized by maximum chemical and physico-chemical selectivity with respect to impurities, chemical inertness to equipment material, container, etc

  6. Enthalpy of interaction between coaggregating and non-coaggregating oral bacterial pairs--a microcalorimetric study.

    Science.gov (United States)

    Postollec, Florence; Norde, Willem; van der Mei, Henny C; Busscher, Henk J

    2003-10-01

    Bacterial adhesion and coaggregation are involved in the development of oral biofilms, called dental plaque. Although various techniques have already been used to study different aspects of these bacterial interactions, microcalorimetry has not yet been applied. This paper describes how isothermal reaction calorimetry can be employed to determine the enthalpy of coaggregation between two oral bacterial pairs. For most biological processes, the enthalpy tends to reach a minimum value, reflecting the most stable state, which is directly related to the heat content of the system. The calorimeter consists of four measuring units where reaction ampoules are filled with 1.5 ml of an Actinomyces naeslundii 147 suspension, while reference ampoules are filled with buffer only. After equilibration at 25 degrees C, 80 microl of a streptococcal suspension was titrated into the reaction ampoules. To study possible saturation of the binding sites on the actinomyces surface, three consecutive injections with streptococcal suspensions were done. Following each injection, a 20-microl aliquot was taken from the ampoule kept outside the calorimeter and the number of free (S(f)) and bound (S(b)) streptococci was determined microscopically. Experiments were carried out with a coaggregating streptococcal strain (Streptococcus oralis J22) and a non-coaggregating strain (Streptococcus sanguis PK1889), serving as a control. The coaggregation enthalpy was exothermic, that is, heat was released in the reaction ampoule upon coaggregation and the heat released by the coaggregating pair minus the heat released by the non-coaggregating pair yielded a coaggregation enthalpy of -0.015 x 10(-6) mJ/bound streptococcus for the first injection. Upon consecutive injections, the coaggregation enthalpy decreased to -0.0004 x 10(-6) mJ/bound streptococcus. Comparison with enthalpy changes reported for lectin-carbohydrate binding suggests that a huge number of binding sites are involved in the formation of

  7. Molecular simulation of excess isotherm and excess enthalpy change in gas-phase adsorption.

    Science.gov (United States)

    Do, D D; Do, H D; Nicholson, D

    2009-01-29

    We present a new approach to calculating excess isotherm and differential enthalpy of adsorption on surfaces or in confined spaces by the Monte Carlo molecular simulation method. The approach is very general and, most importantly, is unambiguous in its application to any configuration of solid structure (crystalline, graphite layer or disordered porous glass), to any type of fluid (simple or complex molecule), and to any operating conditions (subcritical or supercritical). The behavior of the adsorbed phase is studied using the partial molar energy of the simulation box. However, to characterize adsorption for comparison with experimental data, the isotherm is best described by the excess amount, and the enthalpy of adsorption is defined as the change in the total enthalpy of the simulation box with the change in the excess amount, keeping the total number (gas + adsorbed phases) constant. The excess quantities (capacity and energy) require a choice of a reference gaseous phase, which is defined as the adsorptive gas phase occupying the accessible volume and having a density equal to the bulk gas density. The accessible volume is defined as the mean volume space accessible to the center of mass of the adsorbate under consideration. With this choice, the excess isotherm passes through a maximum but always remains positive. This is in stark contrast to the literature where helium void volume is used (which is always greater than the accessible volume) and the resulting excess can be negative. Our definition of enthalpy change is equivalent to the difference between the partial molar enthalpy of the gas phase and the partial molar enthalpy of the adsorbed phase. There is no need to assume ideal gas or negligible molar volume of the adsorbed phase as is traditionally done in the literature. We illustrate this new approach with adsorption of argon, nitrogen, and carbon dioxide under subcritical and supercritical conditions.

  8. Entropy-enthalpy Compensation of Biomolecular Systems in Aqueous Phase: a Dry Perspective.

    Science.gov (United States)

    Movileanu, Liviu; Schiff, Eric A

    2013-01-01

    We survey thermodynamic measurements on processes involving biological macromolecules in aqueous solution, which illustrate well the ubiquitous phenomenon of entropy-enthalpy compensation. The processes include protein folding/unfolding and ligand binding/unbinding, with compensation temperatures varying by about 50 K around an average near 293 K. We show that incorporating both near-exact entropy-enthalpy compensation (due to solvent relaxation) and multi-excitation entropy (from vibrational quanta) leads to a compensation temperature in water of about 230 K. We illustrate a general procedure for subtracting solvent and environment-related terms to determine the bare Gibbs free energy changes of chemical processes.

  9. Plausible Effect of Weather on Atlantic Meridional Overturning Circulation with a Coupled General Circulation Model

    Science.gov (United States)

    Liu, Zedong; Wan, Xiuquan

    2018-04-01

    The Atlantic meridional overturning circulation (AMOC) is a vital component of the global ocean circulation and the heat engine of the climate system. Through the use of a coupled general circulation model, this study examines the role of synoptic systems on the AMOC and presents evidence that internally generated high-frequency, synoptic-scale weather variability in the atmosphere could play a significant role in maintaining the overall strength and variability of the AMOC, thereby affecting climate variability and change. Results of a novel coupling technique show that the strength and variability of the AMOC are greatly reduced once the synoptic weather variability is suppressed in the coupled model. The strength and variability of the AMOC are closely linked to deep convection events at high latitudes, which could be strongly affected by the weather variability. Our results imply that synoptic weather systems are important in driving the AMOC and its variability. Thus, interactions between atmospheric weather variability and AMOC may be an important feedback mechanism of the global climate system and need to be taken into consideration in future climate change studies.

  10. Asymmetric Relationship between the Meridional Displacement of the Asian Westerly Jet and the Silk Road Pattern

    Science.gov (United States)

    Hong, Xiaowei; Lu, Riyu; Li, Shuanglin

    2018-04-01

    In previous work, a significant relationship was identified between the meridional displacement of the Asian westerly jet (JMD) and the Silk Road Pattern (SRP) in summer. The present study reveals that this relationship is robust in northward JMD years but absent in southward JMD years. In other words, the amplitude of the SRP increases with northward displacement of the jet but shows little change with southward displacement. Further analysis indicates that, in northward JMD years, the Rossby wave source (RWS) anomalies, which are primarily contributed by the planetary vortex stretching, are significantly stronger around the entrance of the Asian jet, i.e., the Mediterranean Sea-Caspian Sea area, with the spatial distribution being consistent with that related to the SRP. By contrast, in southward JMD years, the RWS anomalies are much weaker. Therefore, this study suggests that the RWS plays a crucial role in inducing the asymmetry of the JMD-SRP relationship. The results imply that climate anomalies may be stronger in strongly northward-displaced JMD years due to the concurrence of the JMD and SRP, and thus more attention should be paid to these years.

  11. Atmospheric deposition of soluble trace elements along the Atlantic Meridional Transect (AMT)

    Science.gov (United States)

    Baker, Alex R.; Jickells, Tim D.

    2017-11-01

    We briefly review the role of atmospheric deposition measurements within the Atlantic Meridional Transect (AMT) programme and then go on to present new data on the soluble concentrations of a range of trace metals (Fe, Al, Mn, Ti, Zn, V, Ni and Cu) and major ions in aerosols collected along the AMT transect. The results allow us to identify emission sources of the trace metals particularly in terms of the relative importance of anthropogenic versus crustal sources. We identify strong gradients in concentrations and deposition for both crustal and anthropogenically sourced metals with much higher inputs to the North Atlantic compared to the South Atlantic, reflecting stronger land based emission sources in the Northern Hemisphere. We suggest anthropogenic sources of Ni and V may include an important component from shipping. We consider the extent to which these gradients are reflected in surface water concentrations of these metals based on the GEOTRACES water column trace metal data. We find there is a clear difference in the concentrations of surface water dissolved Al and Fe between the north and south Atlantic gyres reflecting atmospheric inputs. However for Mn, V or Ni, higher inputs to the North Atlantic compared to the South Atlantic are not clearly reflected in their water column concentrations.

  12. Interdecadal variability of the meridional overturning circulation as an ocean internal mode

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xiuhua [Universitaet Hamburg, Meteorologisches Institut, Hamburg (Germany); Jungclaus, Johann [Max-Planck-Institut fuer Meteorologie, Hamburg (Germany)

    2008-11-15

    The meridional overturning circulation (MOC) in the coupled ECHAM5/MPIOM exhibits variability at periods of near 30 years and near 60 years. The 30-year variability, referred to as interdecadal variability (IDV), exist in an ocean model driven by climatological atmospheric forcing, suggesting that it is maintained by ocean dynamics; the 60-year variability, the multidecadal variability (MDV), is only observed in the fully coupled model and therefore is interpreted as an atmosphere-ocean coupled mode. The coexistence of the 30-year IDV and the 60-year MDV provides a possible explanation for the widespread time scales observed in climate variables. Further analyses of the climatologically forced ocean model shows that, the IDV is related to the interplay between the horizontal temperature-dominated density gradients and the ocean circulation: temperature anomalies move along the cyclonic subpolar gyre leading to fluctuations in horizontal density gradients and the subsequent weakening and strengthening of the MOC. This result is consistent with that from less complex models, indicating the robustness of the IDV. We further show that, along the North Atlantic Current path, the sea surface temperature anomalies are determined by the slow LSW advection at the intermediate depth. (orig.)

  13. Interdecadal North-Atlantic meridional overturning circulation variability in EC-EARTH

    International Nuclear Information System (INIS)

    Wouters, Bert; Drijfhout, Sybren; Hazeleger, Wilco

    2012-01-01

    The Atlantic meridional overturning circulation (AMOC) in a 600 years pre-industrial run of the newly developed EC-EARTH model features marked interdecadal variability with a dominant time-scale of 50-60 years. An oscillation of approximately 2 Sverdrup (1 Sv = 10 6 m 3 s -1 ) is identified, which manifests itself as a monopole causing the overturning to simultaneously strengthen (/weaken) and deepen (/shallow) as a whole. Eight years before the AMOC peaks, density in the Labrador-Irminger Sea region reaches a maximum, triggering deep water formation. This density change is caused by a counterclockwise advection of temperature and salinity anomalies at lower latitudes, which we relate to the north-south excursions of the subpolar-subtropical gyre boundary and variations in strength and position of the subpolar gyre and the North Atlantic Current. The AMOC fluctuations are not directly forced by the atmosphere, but occur in a delayed response of the ocean to forcing by the North Atlantic Oscillation, which initiates ''intergyre''-gyre fluctuations. Associated with the AMOC is a 60-year sea surface temperature variability in the Atlantic, with a pattern and timescale showing similarities with the real-world Atlantic Multidecadal Variability. This good agreement with observations lends a certain degree of credibility that the mechanism that is described in this article could be seen as representative of the real climate system. (orig.)

  14. Interdecadal North-Atlantic meridional overturning circulation variability in EC-EARTH

    Energy Technology Data Exchange (ETDEWEB)

    Wouters, Bert; Drijfhout, Sybren; Hazeleger, Wilco

    2012-12-15

    The Atlantic meridional overturning circulation (AMOC) in a 600 years pre-industrial run of the newly developed EC-EARTH model features marked interdecadal variability with a dominant time-scale of 50-60 years. An oscillation of approximately 2 Sverdrup (1 Sv = 10{sup 6} m{sup 3} s{sup -1}) is identified, which manifests itself as a monopole causing the overturning to simultaneously strengthen (/weaken) and deepen (/shallow) as a whole. Eight years before the AMOC peaks, density in the Labrador-Irminger Sea region reaches a maximum, triggering deep water formation. This density change is caused by a counterclockwise advection of temperature and salinity anomalies at lower latitudes, which we relate to the north-south excursions of the subpolar-subtropical gyre boundary and variations in strength and position of the subpolar gyre and the North Atlantic Current. The AMOC fluctuations are not directly forced by the atmosphere, but occur in a delayed response of the ocean to forcing by the North Atlantic Oscillation, which initiates ''intergyre''-gyre fluctuations. Associated with the AMOC is a 60-year sea surface temperature variability in the Atlantic, with a pattern and timescale showing similarities with the real-world Atlantic Multidecadal Variability. This good agreement with observations lends a certain degree of credibility that the mechanism that is described in this article could be seen as representative of the real climate system. (orig.)

  15. Meridional circulation in rotating stars. VII. The effects of chemical inhomogeneities

    International Nuclear Information System (INIS)

    Tassoul, M.; Tassoul, J.

    1984-01-01

    In this paper we discuss the effects of a gradient of mean molecular weight μ on the rotationally driven currents that pervade the radiative zone of a single, nonmagnetic, main-sequence star. Detailed numerical calculations are made for the hydrogen-burning core of a solar-type star, assuming that departures from spherical symmetry are not too large. It is found that meridional streaming virtually dies out from the center outward as the μ-gradient grows in a leisurely fashion. This prevents a substantial mixing of matter between the inner (inhomogeneous) and outer (homogeneous) regions in the radiative zone, although the inner region may be penetrated to some degree. To first order in the ratio of the centrifugal force to gravity at the equator, this pattern of circulation is independent of the mean angular velocity. To this order, then, there is no critical rotation rate above which unimpeded mixing may take place. These quantitative results are compared with diverse statements that can be found in the phenomenological literature on rotational mixing

  16. Anelastic Models of Fully-Convective Stars: Differential Rotation, Meridional Circulation and Residual Entropy

    Science.gov (United States)

    Sainsbury-Martinez, Felix; Browning, Matthew; Miesch, Mark; Featherstone, Nicholas A.

    2018-01-01

    Low-Mass stars are typically fully convective, and as such their dynamics may differ significantly from sun-like stars. Here we present a series of 3D anelastic HD and MHD simulations of fully convective stars, designed to investigate how the meridional circulation, the differential rotation, and residual entropy are affected by both varying stellar parameters, such as the luminosity or the rotation rate, and by the presence of a magnetic field. We also investigate, more specifically, a theoretical model in which isorotation contours and residual entropy (σ‧ = σ ‑ σ(r)) are intrinsically linked via the thermal wind equation (as proposed in the Solar context by Balbus in 2009). We have selected our simulation parameters in such as way as to span the transition between Solar-like differential rotation (fast equator + slow poles) and ‘anti-Solar’ differential rotation (slow equator + fast poles), as characterised by the convective Rossby number and △Ω. We illustrate the transition from single-celled to multi-celled MC profiles, and from positive to negative latitudinal entropy gradients. We show that an extrapolation involving both TWB and the σ‧/Ω link provides a reasonable estimate for the interior profile of our fully convective stars. Finally, we also present a selection of MHD simulations which exhibit an almost unsuppressed differential rotation profile, with energy balances remaining dominated by kinetic components.

  17. A coupled model study on the Atlantic Meridional Overturning Circulation under extreme atmospheric CO2 conditions

    Directory of Open Access Journals (Sweden)

    Rita Lecci

    2016-05-01

    Full Text Available This study investigates the climate sensitivity to a strong CO2 atmospheric forcing focusing on the North Atlantic Ocean (NA. The analysis is based on a set of 600 years long experiments performed with a state-of-the-art coupled general circulation model (CGCM with the 1990 reference value of atmospheric CO2 multiplied by 4, 8 and 16. Extreme increases in atmospheric CO2 concentration have been applied to force the climate system towards stable states with different thermo-dynamical properties and analyze how the different resulting oceanic stratification and diffusion affect the Atlantic Meridional Overturning Circulation (AMOC. The AMOC weakens in response to the induced warming with distinctive features in the extreme case: a southward shift of convective sites and the formation of a density front at mid-latitudes. The analysis of the density fluxes reveals that NA loses density at high latitudes and gains it southward of 40°N mainly due to the haline contribution. Our results indicate that the most important processes that control the AMOC are active in the high latitudes and are related to the stability of the water column. The increased ocean stratification stabilizes the ocean interior leading to a decreased vertical diffusivity, a reduction in the formation of deep water and a weaker circulation. In particular, the deep convection collapses mainly in the Labrador Sea as a consequence of the water column stratification under high latitudes freshening.

  18. Reduced interdecadal variability of Atlantic Meridional Overturning Circulation under global warming

    Science.gov (United States)

    Cheng, Jun; Liu, Zhengyu; Zhang, Shaoqing; Liu, Wei; Dong, Lina; Liu, Peng; Li, Hongli

    2016-01-01

    Interdecadal variability of the Atlantic Meridional Overturning Circulation (AMOC-IV) plays an important role in climate variation and has significant societal impacts. Past climate reconstruction indicates that AMOC-IV has likely undergone significant changes. Despite some previous studies, responses of AMOC-IV to global warming remain unclear, in particular regarding its amplitude and time scale. In this study, we analyze the responses of AMOC-IV under various scenarios of future global warming in multiple models and find that AMOC-IV becomes weaker and shorter with enhanced global warming. From the present climate condition to the strongest future warming scenario, on average, the major period of AMOC-IV is shortened from ∼50 y to ∼20 y, and the amplitude is reduced by ∼60%. These reductions in period and amplitude of AMOC-IV are suggested to be associated with increased oceanic stratification under global warming and, in turn, the speedup of oceanic baroclinic Rossby waves. PMID:26951654

  19. Equinoctial asymmetry of a low-latitude ionosphere-thermosphere system and equatorial irregularities: evidence for meridional wind control

    Directory of Open Access Journals (Sweden)

    T. Maruyama

    2009-05-01

    Full Text Available Nocturnal ionospheric height variations were analyzed along the meridian of 100° E by using ionosonde data. Two ionosondes were installed near the magnetic conjugate points at low latitudes, and the third station was situated near the magnetic equator. Ionospheric virtual heights were scaled every 15 min and vertical E×B drift velocities were inferred from the equatorial station. By incorporating the inferred equatorial vertical drift velocity, ionospheric bottom heights with the absence of wind were modeled for the two low-latitude conjugate stations, and the deviation in heights from the model outputs was used to infer the transequatorial meridional thermospheric winds. The results obtained for the September and March equinoxes of years 2004 and 2005, respectively, were compared, and a significant difference in the meridional wind was found. An oscillation with a period of approximately 7 h of the meridional wind existed in both the equinoxes, but its amplitude was larger in September as compared to that in March. When the equatorial height reached the maximum level due to the evening enhancement of the zonal electric field, the transequatorial meridional wind velocity reached approximately 10 and 40 m/s for the March and September equinoxes, respectively. This asymmetry of the ionosphere-thermosphere system was found to be associated with the previously reported equinoctial asymmetry of equatorial ionospheric irregularities; the probability for equatorial irregularities to occur is higher in March as compared to that in September at the Indian to Western Pacific longitudes. Numerical simulations of plasma bubble developments were conducted by incorporating the transequatorial neutral wind effect, and the results showed that the growth time (e-folding time of the bubble was halved when the wind velocity changed from 10 to 40 m/s.

  20. The role of the meridional sea surface temperature gradient in controlling the Caribbean low-level jet

    Science.gov (United States)

    Maldonado, Tito; Rutgersson, Anna; Caballero, Rodrigo; Pausata, Francesco S. R.; Alfaro, Eric; Amador, Jorge

    2017-06-01

    The Caribbean low-level jet (CLLJ) is an important modulator of regional climate, especially precipitation, in the Caribbean and Central America. Previous work has inferred, due to their semiannual cycle, an association between CLLJ strength and meridional sea surface temperature (SST) gradients in the Caribbean Sea, suggesting that the SST gradients may control the intensity and vertical shear of the CLLJ. In addition, both the horizontal and vertical structure of the jet have been related to topographic effects via interaction with the mountains in Northern South America (NSA), including funneling effects and changes in the meridional geopotential gradient. Here we test these hypotheses, using an atmospheric general circulation model to perform a set of sensitivity experiments to examine the impact of both SST gradients and topography on the CLLJ. In one sensitivity experiment, we remove the meridional SST gradient over the Caribbean Sea and in the other, we flatten the mountains over NSA. Our results show that the SST gradient and topography have little or no impact on the jet intensity, vertical, and horizontal wind shears, contrary to previous works. However, our findings do not discount a possible one-way coupling between the SST and the wind over the Caribbean Sea through friction force. We also examined an alternative approach based on barotropic instability to understand the CLLJ intensity, vertical, and horizontal wind shears. Our results show that the current hypothesis about the CLLJ must be reviewed in order to fully understand the atmospheric dynamics governing the Caribbean region.

  1. The Calculation of Standard Enthalpies of Formation of Alkanes: Illustrating Molecular Mechanics and Spreadsheet Programs

    Science.gov (United States)

    Hawk, Eric Leigh

    1999-02-01

    How group increment methods may be used to predict standard enthalpies of formation of alkanes is outlined as an undergraduate computational chemistry experiment. The experiment requires input and output data sets. Although users may create their own data sets, both sets are provided. The input data set contains experimentally determined gas-phase standard enthalpies of formation and calculated steric energies for 10 alkanes. The steric energy for an alkane is calculated via a Molecular Mechanics approach employing Allinger's MM3 force field. Linear regression analysis on data contained in the input data set generates the coefficients that are used with the output data set to calculate standard enthalpies of formation for 15 alkanes. The average absolute error for the calculated standard enthalpies of formation is 1.22 kcal/mol. The experiment is highly suited to those interested in incorporating more computational chemistry in their curricula. In this regard, it is ideally suited for a physical chemistry laboratory, but it may be used in an organic chemistry course as well.

  2. The relation between relaxed enthalpy and volume during physical aging of amorphous polymers and selenium

    Czech Academy of Sciences Publication Activity Database

    Slobodian, P.; Říha, Pavel; Rychwalski, R. W.; Emri, I.; Sáha, P.; Kubát, J.

    2006-01-01

    Roč. 42, č. 10 (2006), s. 2824-2837 ISSN 0014-3057 R&D Projects: GA AV ČR IAA2060401 Institutional research plan: CEZ:AV0Z20600510 Keywords : Enthalpy relaxation * Polymer aging Subject RIV: BJ - Thermodynamics Impact factor: 2.113, year: 2006

  3. Heat capacty, relative enthalpy, and calorimetric entropy of silicate minerals: an empirical method of prediction.

    Science.gov (United States)

    Robinson, G.R.; Haas, J.L.

    1983-01-01

    Through the evaluation of experimental calorimetric data and estimates of the molar isobaric heat capacities, relative enthalpies and entropies of constituent oxides, a procedure for predicting the thermodynamic properties of silicates is developed. Estimates of the accuracy and precision of the technique and examples of its application are also presented. -J.A.Z.

  4. Investigation of enthalpy and specific heat of the gallium-indium-tin eutectic alloy

    International Nuclear Information System (INIS)

    Roshchupkin, V.V.; Migaj, L.L.; Fordeeva, L.K.; Perlova, N.L.

    1978-01-01

    Enthalpy and specific heat of the fusible (melting point is 10.6 deg C) eutectic alloy (67% Ga - 20.5% In - 12.5% Sn according to mass) are determined by the mixing method. The determination was carried out in vacuum at the residual pressure of >= 1x10 -5 torr in the temperature range from 59.3 to 437.0 deg C. It is established that temperature dependence of alloy enthalpy is described by the equation: Hsub(t) - Hsub(0degC)=1.014+0.0879t-0.0000129 t 2 , where (Hsub(t) - Hsub(0degC)) is enthalpy, cal/g; t-temperature, deg C. Mean-square dispersion is +-0.6%. Temperature dependence of alloy specific heat in the temperature range under study was determined by differentiation of the equation obtained for enthalpy: Csub(p)=0.0879-0.000026t, where Csub(p)-specific heat, cal/gx deg. It is supposed that temperature increase makes it possible to decrease slightly specific heat

  5. Melting point gram-atomic volumes and enthalpies of atomization for liquid elements

    International Nuclear Information System (INIS)

    Lamoreaux, R.H.

    1976-01-01

    Values of the gram-atomic volumes and enthalpies of atomization to the monatomic ideal gas state for liquid elements at their melting points are collected to facilitate predictions of the behavior of mixed systems. Estimated values are given for experimentally undetermined quantities

  6. Enthalpy of mixing of liquid Cu-Fe-Hf alloys at 1873 K

    Energy Technology Data Exchange (ETDEWEB)

    Agraval, Pavel; Turchanin, Mikhail [Donbass State Engineering Academy, Kramatorsk (Ukraine). Metallurgical Dept.; Dreval, Liya [Donbass State Engineering Academy, Kramatorsk (Ukraine). Metallurgical Dept.; Materials Science International Services GmbH (MSI), Stuttgart (Germany)

    2016-12-15

    In the ternary Cu-Fe-Hf system, the mixing enthalpies of liquid alloys were investigated at 1873 K using a high-temperature isoperibolic calorimeter. The experiments were performed along the sections x{sub Cu}/x{sub Fe} = 3/1, 1/1 at x{sub Hf} = 0-0.47 and along the section x{sub Cu}/x{sub Fe} = 1/3 at x{sub Hf} = 0-0.13. The limiting partial enthalpies of mixing of undercooled liquid hafnium in liquid Cu-Fe alloys, Δ{sub mix} anti H{sub Hf}{sup ∞}, are (-122 ± 9) kJ mol{sup -1} (section x{sub Cu}/x{sub Fe} = 3/1), (-106 ± 9) kJ mol{sup -1} (section x{sub Cu}/x{sub Fe} = 1/1), and (-105 ± 2) kJ mol{sup -1} (section x{sub Cu}/x{sub Fe} = 1/3). In the investigated composition range, the integral mixing enthalpies are sign-changing. For the integral mixing enthalpy, an analytical expression was obtained by the least squares fit of the experimental results using the Redlich-Kister-Muggianu polynomial.

  7. Enthalpy relaxations in polymer blends and block copolymers : Influence of domain size

    NARCIS (Netherlands)

    Brinke, G. ten; Grooten, R.

    1989-01-01

    It is now well known that enthalpy relaxation measurements can be used to establish polymer-polymer blend phase behavior when the glass transition temperatures of the two polymers are virtually coincident. In the most simple cases, the aging kinetics of an immiscible blend will be representative of

  8. The thermal characterization of multi-component systems by enthalpy relaxation

    NARCIS (Netherlands)

    Brinke, Gerrit ten; Oudhuis, Lizette; Ellis, Thomas S.

    1994-01-01

    The phenomenon of enthalpy relaxation of amorphous glassy polymers has been developed into an analytical tool which can be applied to elucidate phase behavior and morphologically related phenomena of multi-component systems. We have both reviewed the experimental details concerning its application,

  9. Behavior of the Enthalpy of Adsorption in Nanoporous Materials close to Saturation Conditions

    NARCIS (Netherlands)

    Torres-Knoop, Ariana; Poursaeidesfahani, A.; Vlugt, T.J.H.; Dubbeldam, D.

    2017-01-01

    Many important industrial separation processes based on adsorption operate close to saturation. In this regime, the underlying adsorption processes are mostly driven by entropic forces. At equilibrium, the entropy of adsorption is closely related to the enthalpy of adsorption. Thus, studying the

  10. Problem-Based Learning in Teaching Chemistry: Enthalpy Changes in Systems

    Science.gov (United States)

    Ayyildiz, Yildizay; Tarhan, Leman

    2018-01-01

    Background: Problem-based learning (PBL) as a teaching strategy has recently become quite widespread in especially chemistry classes. Research has found that students, from elementary through college, have many alternative conceptions regarding "enthalpy changes in systems." Although there are several studies focused on identifying…

  11. Enthalpy-driven interactions with sulfated glycosaminoglycans promote cell membrane penetration of arginine peptides.

    Science.gov (United States)

    Takechi-Haraya, Yuki; Nadai, Ryo; Kimura, Hitoshi; Nishitsuji, Kazuchika; Uchimura, Kenji; Sakai-Kato, Kumiko; Kawakami, Kohsaku; Shigenaga, Akira; Kawakami, Toru; Otaka, Akira; Hojo, Hironobu; Sakashita, Naomi; Saito, Hiroyuki

    2016-06-01

    The first step of cell membrane penetration of arginine peptides is thought to occur via electrostatic interactions between positive charges of arginine residues and negative charges of sulfated glycosaminoglycans (GAGs) on the cell surface. However, the molecular interaction of arginine peptides with GAG still remains unclear. Here, we compared the interactions of several arginine peptides of Tat, R8, and Rev and their analogues with heparin in relation to the cell membrane penetration efficiency. The high-affinity binding of arginine peptides to heparin was shown to be driven by large favorable enthalpy contributions, possibly reflecting multidentate hydrogen bondings of arginine residues with sulfate groups of heparin. Interestingly, the lysine peptides in which all arginine residues are substituted with lysine residues exhibited negligible binding enthalpy despite of their considerable binding to heparin. In CHO-K1 cells, arginine peptides exhibited a great cell-penetrating ability whereas their corresponding lysine peptides did not penetrate into cells. The degree of cell penetration of arginine peptides markedly decreased by the chlorate treatment of cells which prevents the sulfation of GAG chains. Significantly, the cell penetration efficiency of arginine peptides was found to be correlated with the favorable enthalpy of binding to heparin. These results suggest that the enthalpy-driven strong interaction with sulfated GAGs such as heparan sulfate plays a critical role in the efficient cell membrane penetration of arginine peptides. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. The Correlation of Standard Entropy with Enthalpy Supplied from 0 to 298.15 K

    Science.gov (United States)

    Lambert, Frank L.; Leff, Harvey S.

    2009-01-01

    As a substance is heated at constant pressure from near 0 K to 298 K, each incremental enthalpy increase, dH, alters entropy by dH/T, bringing it from approximately zero to its standard molar entropy S degrees. Using heat capacity data for 32 solids and CODATA results for another 45, we found a roughly linear relationship between S degrees and…

  13. Hydrogen Bonding Interactions and Enthalpy Relaxation in Sugar/Protein Glasses.

    Science.gov (United States)

    Sydykov, Bulat; Oldenhof, Harriëtte; Sieme, Harald; Wolkers, Willem F

    2017-03-01

    In this study, hydrogen bonding interactions and enthalpy relaxation phenomena of sugar and sugar/protein glasses have been studied using Fourier transform infrared spectroscopy and differential scanning calorimetry. The sugar OH band in Fourier transform infrared spectra was used to derive the glass transition temperature, T g , and the wavenumber-temperature coefficient (WTC) of the OH band. A study on mixtures of sucrose and albumin revealed that the glass transition temperature and strength of hydrogen bonds increased with increasing percentages of albumin. WTC g and T g derived from sucrose/albumin glasses showed a negative linear correlation. The Lu-Weiss equation was used to fit T g data of sucrose/albumin mixtures. An inflection point was observed at a 1:1 mass ratio, which coincided with an inflection of the OH-stretching band denoting a change in hydrogen bonding interactions. Enthalpy relaxation, which is seen as an endothermic event superimposed on the glass transition in differential scanning calorimetry thermograms, increases with increasing storage temperature. Activation energies of enthalpy relaxation of sucrose and sucrose/albumin glasses were determined to be 332 and 236 kJ mol -1 , respectively. Addition of albumin to sucrose increases the T g , average strength of hydrogen bonding, heterogeneity, and the enthalpy relaxation time, making the glass more stable during storage at room temperature. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  14. The Relationship between Lattice Enthalpy and Melting Point in Magnesium and Aluminium Oxides. Science Notes

    Science.gov (United States)

    Talbot, Christopher; Yap, Lydia

    2013-01-01

    This "Science Note" presents a study by Christopher Talbot and Lydia Yap, who teach IB Chemistry at Anglo-Chinese School (Independent), Republic of Singapore, to pre-university students. Pre-university students may postulate the correlation between the magnitude of the lattice enthalpy compound and its melting point, since both…

  15. Enthalpy of mixing of liquid Ag–Bi–Cu alloys at 1073 K

    International Nuclear Information System (INIS)

    Fima, Przemysław; Flandorfer, Hans

    2014-01-01

    Highlights: • Partial and integral mixing enthalpies of liquid Ag–Bi–Cu alloys were determined. • Integral mixing enthalpies are small and endothermic, similar to limiting binaries. • The ternary data were fitted on the basis of Redlich–Kister–Muggianu model. - Abstract: The Ag–Bi–Cu system is among those ternary systems which have not been fully studied yet, in particular the thermodynamic description of the liquid phase is missing. Partial and integral enthalpies of mixing of liquid ternary Ag–Bi–Cu alloys were determined over a broad composition range along six sections: x(Ag)/x(Bi) = 0.25, 1, 4; x(Ag)/x(Cu) = 1.5; x(Bi)/x(Cu) = 1.86, 4. Measurements were carried out at 1073 K using two Calvet type microcalorimeters and drop calorimetric technique. It was found that integral enthalpies of mixing are small and endothermic, similarly to limiting binary alloys. The ternary data were fitted on the basis of an extended Redlich–Kister–Muggianu model for substitutional solutions. There are no significant additional ternary interactions

  16. The Evaluation of Empirical Resonance Energies as Reaction Enthalpies with Particular Reference to Benzene.

    Science.gov (United States)

    George, Philip; And Others

    1984-01-01

    Discusses the nature of experimental resonance energy, explaining how its magnitude depends upon choice of reference molecules from which bond energies are derived. Also explains how it can be evaluated more simply, without recourse to bond energies, as enthalpy change for a reaction predetermined by choice of reference molecules. (JN)

  17. Fractured Anhydrite as a Geothermal Source in a Low Enthalpy Context (Southern Permian Basin, Netherlands)

    NARCIS (Netherlands)

    Daniilidis, Alexandros; Herber, Marinus

    2015-01-01

    Increased heat flow associated with the presence of salt domes could be beneficial for geothermal energy applications in a low enthalpy nvironment. Anhydrite layers within such salt domes could be a potential geothermal target. These layers are known to undergo brittle deformation, which in turn can

  18. Coupling geophysical investigation with hydrothermal modeling to constrain the enthalpy classification of a potential geothermal resource.

    Science.gov (United States)

    White, Jeremy T.; Karakhanian, Arkadi; Connor, Chuck; Connor, Laura; Hughes, Joseph D.; Malservisi, Rocco; Wetmore, Paul

    2015-01-01

    An appreciable challenge in volcanology and geothermal resource development is to understand the relationships between volcanic systems and low-enthalpy geothermal resources. The enthalpy of an undeveloped geothermal resource in the Karckar region of Armenia is investigated by coupling geophysical and hydrothermal modeling. The results of 3-dimensional inversion of gravity data provide key inputs into a hydrothermal circulation model of the system and associated hot springs, which is used to evaluate possible geothermal system configurations. Hydraulic and thermal properties are specified using maximum a priori estimates. Limited constraints provided by temperature data collected from an existing down-gradient borehole indicate that the geothermal system can most likely be classified as low-enthalpy and liquid dominated. We find the heat source for the system is likely cooling quartz monzonite intrusions in the shallow subsurface and that meteoric recharge in the pull-apart basin circulates to depth, rises along basin-bounding faults and discharges at the hot springs. While other combinations of subsurface properties and geothermal system configurations may fit the temperature distribution equally well, we demonstrate that the low-enthalpy system is reasonably explained based largely on interpretation of surface geophysical data and relatively simple models.

  19. Relationship between Standard Enthalpies/Entropies of Formation and Topological Structural Characteristics for Saturated Hydrocarbons

    Science.gov (United States)

    Dolomatov, M. Yu.; Aubekerov, T. M.

    2018-03-01

    QSPR models are proposed that satisfactorily describe the relationships between standard enthalpies/ entropies of formation and topological indices in the form of Wiener and Randić indices and the sum of the squares of the eigenvalues from the adjacency matrix of a molecular graph. The models can be recommended for use in scientific and engineering calculations of thermodynamic functions.

  20. Enthalpy measurement of lithium meta-titanate by drop calorimetry and its derived heat capacity

    International Nuclear Information System (INIS)

    Ishioka, Rika; Mukai, Keisuke; Terai, Takayuki; Suzuki, Akihiro

    2013-01-01

    Highlights: • Li 2 TiO 3 was synthesized by a neutralizing method. • Enthalpy of Li 2 TiO 3 was measured by a drop calorimeter. • Heat capacity of Li 2 TiO 3 was derived as a function of temperature. -- Abstract: Enthalpy of Li 2 TiO 3 , which was synthesized by a neutralizing method and its Li/Ti ratio was determined to be Li/Ti ratio (mol/mol) = 1.97, was measured by a drop calorimeter, and its heat capacity was derived as a function of temperature. XRD (X-ray diffraction) analysis of the sample before and after the enthalpy measurement indicated no phase change during the measurement and a single phase of Li 2 TiO 3 was observed. The enthalpy data were expressed as H(T) − H(323.17) (J/g) = 2.2 × 10 −5 ·T 2 + 1.4·T + 2.7 × 10 4 /T − 5.6 × 10 2 (373–1273 K), where T is temperature in K. The heat capacity was calculated as C p (J/g K) = 2.2 × 2 × 10 −5 ·T + 1.4–2.7 × 10 4 /T 2 by differentiating the equation by temperature. These equations have accuracy of 3%

  1. Enthalpy-based equation of state for highly porous materials employing modified soft sphere fluid model

    Science.gov (United States)

    Nayak, Bishnupriya; Menon, S. V. G.

    2018-01-01

    Enthalpy-based equation of state based on a modified soft sphere model for the fluid phase, which includes vaporization and ionization effects, is formulated for highly porous materials. Earlier developments and applications of enthalpy-based approach had not accounted for the fact that shocked states of materials with high porosity (e.g., porosity more than two for Cu) are in the expanded fluid region. We supplement the well known soft sphere model with a generalized Lennard-Jones formula for the zero temperature isotherm, with parameters determined from cohesive energy, specific volume and bulk modulus of the solid at normal condition. Specific heats at constant pressure, ionic and electronic enthalpy parameters and thermal excitation effects are calculated using the modified approach and used in the enthalpy-based equation of state. We also incorporate energy loss from the shock due to expansion of shocked material in calculating porous Hugoniot. Results obtained for Cu, even up to initial porosities ten, show good agreement with experimental data.

  2. Thermodynamic and transport properties of fluids

    Science.gov (United States)

    Fessler, T. E.

    1980-01-01

    Computer program subroutine FLUID calculates thermodynamic and transport properties of pure fluids in liquid, gas, or two-phase (liquid/gas) conditions. Program determines thermodynamic state from assigned values for temperature and density, pressure and density, temperature and pressure, pressure and entropy, or pressure and enthalpy.

  3. Application of the numerical density-enthalpy method to the multi-phase flow through a porous medium

    NARCIS (Netherlands)

    Ibrahim, D.; Vermolen, F.J.; Vuik, C.

    2010-01-01

    In this paper we apply a new method to solve multi-phase fluid flow problem for 1D1D and 2D2D fluid systems. This method is developed at TNO and presented in [1] for spatially homogeneous systems. We call this method the numerical density-enthalpy method (or ??-hh method) because density-enthalpy

  4. Standard formation enthalpies of Nasub(2+x)Vsub(6)Osub(16-y) bronze of kappa type

    International Nuclear Information System (INIS)

    Khodos, M.Ya.; Slobodin, B.V.; Surat, L.L.; Fotiev, A.A.

    1980-01-01

    Standard formation enthalpies of sodium oxide vanadium bronze of kappa Nasub(2+x)Vsub(6)Osub(16-y) type of different composition have been determined by the method of solution calorimetry. It has been ascertained that within the limits of homogeneity a standard formation enthalpy decreases insignificantly with the increase of bronze oxygen defectiveness and is a linear function of sodium content

  5. Preliminary Results from Electric Arc Furnace Off-Gas Enthalpy Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Nimbalkar, Sachin U [ORNL; Thekdi, Arvind [E3M Inc; Keiser, James R [ORNL; Storey, John Morse [ORNL

    2015-01-01

    This article describes electric arc furnace (EAF) off-gas enthalpy models developed at Oak Ridge National Laboratory (ORNL) to calculate overall heat availability (sensible and chemical enthalpy) and recoverable heat values (steam or power generation potential) for existing EAF operations and to test ORNL s new EAF waste heat recovery (WHR) concepts. ORNL s new EAF WHR concepts are: Regenerative Drop-out Box System and Fluidized Bed System. The two EAF off-gas enthalpy models described in this paper are: 1.Overall Waste Heat Recovery Model that calculates total heat availability in off-gases of existing EAF operations 2.Regenerative Drop-out Box System Model in which hot EAF off-gases alternately pass through one of two refractory heat sinks that store heat and then transfer it to another gaseous medium These models calculate the sensible and chemical enthalpy of EAF off-gases based on the off-gas chemical composition, temperature, and mass flow rate during tap to tap time, and variations in those parameters in terms of actual values over time. The models provide heat transfer analysis for the aforementioned concepts to confirm the overall system and major component sizing (preliminary) to assess the practicality of the systems. Real-time EAF off-gas composition (e.g., CO, CO2, H2, and H2O), volume flow, and temperature data from one EAF operation was used to test the validity and accuracy of the modeling work. The EAF off-gas data was used to calculate the sensible and chemical enthalpy of the EAF off-gases to generate steam and power. The article provides detailed results from the modeling work that are important to the success of ORNL s EAF WHR project. The EAF WHR project aims to develop and test new concepts and materials that allow cost-effective recovery of sensible and chemical heat from high-temperature gases discharged from EAFs.

  6. Determination of the protonation enthalpy of humic acid by calorimetric titration technique

    International Nuclear Information System (INIS)

    Kimuro, Shingo; Kirishima, Akira; Sato, Nobuaki

    2015-01-01

    Graphical abstract: The thermodynamic quantities of protonation of humic acid were determined by the combination of potentiometric titration and calorimetric titration. It was observed that the protonation enthalpy and Gibbs free energy had been affected by pH of solution. As a result, the thermodynamics of the protonation reaction of humic acid is influenced by the polyelectrolyte effect and the heterogeneity. - Highlights: • We applied calorimetric titration technique to the protonation of humic acid. • The thermodynamic quantities of protonation of humic acid were determined. • The protonation enthalpy of humic acid is affected by the heterogeneity. • Gibbs free energy of the protonation is affected by the polyelectrolyte effect. - Abstract: In this study, the calorimetric titration technique was used to determine the protonation enthalpy of two reference humic acids and polyacrylic acid. First, we obtained the apparent protonation constant of two kinds of humic acid purchased from IHSS (International Humic Substances Society) and polyacrylic acid by potentiometric titration. Second, we obtained the protonation enthalpy of them by calorimetric titration. The protonation enthalpy of humic acid was affected by pH and the ionic strength of bulk solution. From the comparison of ΔH between humic acid and polyacrylic acid, it was concluded that the pH dependence of ΔH is attributed to the heterogeneity of humic acid. And ΔH of phenolic hydroxyl group in humic acid is strongly influenced by the electric double layer of humic acid’s surface. This is considered to be a reason of the ionic strength dependence of ΔH. On the other hand, Gibbs free energy of the protonation of humic acid is affected by the electrostatic attraction with the progress of dissociation of functional groups such as carboxyl group and phenolic hydroxyl group. Consequently, the thermodynamics of the protonation of humic acid is affected by the polyelectrolyte effect and the

  7. The Atlantic Meridional Overturning Circulation over time: a Nd isotope perspective

    Science.gov (United States)

    Goldstein, S. L.; Pena, L. D.; Yehudai, M.; Seguí, M. J.; Kim, J.; Knudson, K. P.; Basak, C.

    2017-12-01

    The Atlantic Meridional Overturning Circulation (AMOC) is a major means for distributing heat between the tropics and the high latitudes, and thus its temporal variability has major impacts on ice age cycles. We present a summary of work in-progress to generate north-south profiles of the AMOC from the North Atlantic to the Southern Ocean, at various time slices over the past 2 Ma, based on Nd isotopes in Fe-Mn oxide encrusted foraminifera and fish debris. Our sites show a consistent north-south gradient in the North Atlantic source water (NSW) signal strength throughout, providing strong evidence that the data represent the fluctuations of the AMOC. The North Atlantic data show strong evidence that the eNd of the NSW end-member remained similar to today through this time interval (Kim et al. this meeting). We have identified 5 modes of the AMOC circulation. The most common ones are the (1) "interglacial norm" where the NSW signal remains strong into the South Atlantic similar to the present-day, and the (2) "glacial norm" where moderate southern source water (SSW) signals extend into the deep North Atlantic. Less common are the (3) "weak AMOC" mode, typical of Heinrich events, the Mid-Pleistocene Transition (MPT), and MIS 10,16, where even the deep North Atlantic shows a strong SSW signal, and its counterpart the (4) "ultra-strong AMOC", in MIS 9, 11, 19, 21 and 25, when the NSW signal is unusually strong south of the equator. Finally, during the (5) "pre-MPT" mode, in MIS 26 and 27, uniquely low Nd isotope ratios in the North Atlantic signals major input of Nd from the Canadian Shield directly preceding the MPT AMOC crisis (Pena and Goldstein, Science 2014), reflecting events there that likely triggered it. Overall we expect that the AMOC profiles will be useful as a means to directly relate climate to concurrent ocean circulation through time.

  8. Variations of the Atlantic meridional overturning circulation in control and transient simulations of the last millennium

    Directory of Open Access Journals (Sweden)

    D. Hofer

    2011-02-01

    Full Text Available The variability of the Atlantic meridional overturing circulation (AMOC strength is investigated in control experiments and in transient simulations of up to the last millennium using the low-resolution Community Climate System Model version 3. In the transient simulations the AMOC exhibits enhanced low-frequency variability that is mainly caused by infrequent transitions between two semi-stable circulation states which amount to a 10 percent change of the maximum overturning. One transition is also found in a control experiment, but the time-varying external forcing significantly increases the probability of the occurrence of such events though not having a direct, linear impact on the AMOC. The transition from a high to a low AMOC state starts with a reduction of the convection in the Labrador and Irminger Seas and goes along with a changed barotropic circulation of both gyres in the North Atlantic and a gradual strengthening of the convection in the Greenland-Iceland-Norwegian (GIN Seas. In contrast, the transition from a weak to a strong overturning is induced by decreased mixing in the GIN Seas. As a consequence of the transition, regional sea surface temperature (SST anomalies are found in the midlatitude North Atlantic and in the convection regions with an amplitude of up to 3 K. The atmospheric response to the SST forcing associated with the transition indicates a significant impact on the Scandinavian surface air temperature (SAT in the order of 1 K. Thus, the changes of the ocean circulation make a major contribution to the Scandinavian SAT variability in the last millennium.

  9. Multi-point optimization on meridional shape of a centrifugal pump impeller for performance improvement

    International Nuclear Information System (INIS)

    Pei, Ji; Wang, Wen Jie; Yuan, Shouqi

    2016-01-01

    A wide operating band is important for a pump to safely perform at maximum efficiency while saving energy. To widen the operating range, a multi-point optimization process based on numerical simulations in order to improve impeller performance of a centrifugal pump used in nuclear plant applications is proposed by this research. The Reynolds average Navier Stokes equations are utilized to perform the calculations. The meridional shape of the impeller was optimized based on the following four parameters; shroud arc radius, hub arc radius, shroud angle, and hub angle as the design variables. Efficiencies calculated under 0.6Qd, 1.0Qd and 1.62Qd were selected as the three optimized objectives. The Design of experiment method was applied to generate various impellers while 35 impellers were generated by the Latin hypercube sampling method. A Response surface function based on a second order function was applied to construct a mathematical relationship between the objectives and design variables. A multi-objective genetic algorithm was utilized to solve the response surface function to obtain the best optimized objectives as well as the best combination of design parameters. The results indicated that the pump performance predicted by numerical simulation was in agreement with the experimental performance. The optimized efficiencies based on the three operating conditions were increased by 3.9 %, 6.1 % and 2.6 %, respectively. In addition, the velocity distribution, pressure distribution, streamline and turbulence kinetic energy distribution of the optimized and reference impeller were compared and analyzed to illustrate the performance improvement

  10. Estudios sobre la vegetación del estado de Paraná (Brasil meridional

    Directory of Open Access Journals (Sweden)

    de Bolòs, Oriol

    1991-12-01

    Full Text Available Contribution to knowledge about the vegetation of the state of Paraná in southern Brazil (Serra do Mar, Planaltos, Iguaçu Valley. Numerous plant associations are described and grouped together in the following classes: Pistio-Eichhornietea (communities of floating cormophytes Xyrido-Typhetea (helophytic herbaceous vegetation Polypodio-Tillandsietea (epiphytic and comophytic vegetation Ruderali-Manihotetea (ruderal and segetal vegetation Andropogono-Baccharidetea (savanoid vegetation Rhizophoretea (mangroves Lantano-Chusqueetea (woody marginal communities of the forest Cedrelo-Ocoteetea (rain and mesophilous forest. Special attention is paid to the study of the physiognomy, structure and dynamism of the vegetation and its biogeographical significance.

    Aportación al conocimiento de la vegetación del estado de Paraná en el Brasil meridional (Serra do Mar, Planaltos, valle del Iguaçu. Se describen numerosas asociaciones vegetales agrupadas en las clases siguientes: Pistio-Eichhornietea (comunidades de cormófitos flotantes. Xyrido-Typhetea (vegetación herbácea helofítica. Polypodio-Tillandsietea (vegetación epifítica y comofítica. Ruderali-Manihotetea (vegetación ruderal, viaria y arvense. Andropogono-Baccharidetea (vegetación sabanoide. Rhizophoretea (manglar. Lantano-Chusqueetea (manto marginal leñoso de la selva. Cedrelo-Ocoteetea (selva pluvial y mesófila. Se dedica atención especial al estudio de la fisionomía, estructura y dinamismo de la vegetación y a su significación biogeográfica.

  11. Surface ocean carbon dioxide during the Atlantic Meridional Transect (1995-2013); evidence of ocean acidification

    Science.gov (United States)

    Kitidis, Vassilis; Brown, Ian; Hardman-Mountford, Nicholas; Lefèvre, Nathalie

    2017-11-01

    Here we present more than 21,000 observations of carbon dioxide fugacity in air and seawater (fCO2) along the Atlantic Meridional Transect (AMT) programme for the period 1995-2013. Our dataset consists of 11 southbound and 2 northbound cruises in boreal autumn and spring respectively. Our paper is primarily focused on change in the surface-ocean carbonate system during southbound cruises. We used observed fCO2 and total alkalinity (TA), derived from salinity and temperature, to estimate dissolved inorganic carbon (DIC) and pH (total scale). Using this approach, estimated pH was consistent with spectrophotometric measurements carried out on 3 of our cruises. The AMT cruises transect a range of biogeographic provinces where surface Chlorophyll-α spans two orders of magnitude (mesotrophic high latitudes to oligotrophic subtropical gyres). We found that surface Chlorophyll-α was negatively correlated with fCO2, but that the deep chlorophyll maximum was not a controlling variable for fCO2. Our data show clear evidence of ocean acidification across 100° of latitude in the Atlantic Ocean. Over the period 1995-2013 we estimated annual rates of change in: (a) sea surface temperature of 0.01 ± 0.05 °C, (b) seawater fCO2 of 1.44 ± 0.84 μatm, (c) DIC of 0.87 ± 1.02 μmol per kg and (d) pH of -0.0013 ± 0.0009 units. Monte Carlo simulations propagating the respective analytical uncertainties showed that the latter were < 5% of the observed trends. Seawater fCO2 increased at the same rate as atmospheric CO2.

  12. MAPEAMENTO DE UNIDADES DE RELEVO NA MÉDIA SERRA DO ESPINHAÇO MERIDIONAL - MG

    Directory of Open Access Journals (Sweden)

    Éric Andrade Rezende

    2011-04-01

    Full Text Available O presente trabalho propõe um mapeamento de unidades de relevo para a porção sul do terço médio da Serra do Espinhaço Meridional. As unidades de relevo foram delimitadas a partir da análise integrada de cartas temáticas e imagens de satélite que permitiram observar variações na morfologia, na altimetria, na declividade, na litoestrutura e na organização da rede de drenagem. A etapa de cartografia digital, processada no software ArcGis 9.2, se baseou na utilização de produtos SRTM (Shuttle Radar Topography Mission. Os procedimentos metodológicos também incluíram trabalhos de campo e pesquisa bibliográfica. Foi empregada a taxonomia do mapeamento geomorfológico proposta pelo IBGE (2009, através da qual foram individualizadas quatorze Unidades Geomorfológicas. As unidades estão distribuídas entre cinco diferentes compartimentos do seguinte modo: dois planaltos, duas escarpas, seis depressões, três conjuntos de cristas e um conjunto de patamares. Foi possível observar que a disposição geral das unidades reflete o forte controle litoestrutural imposto ao relevo regional. Destaca-se a resistência diferenciada das diversas litologias frente aos processos denudacionais e a influência da neotectônica na geomorfogênese.

  13. Modified solution calorimetry approach for determination of vaporization and sublimation enthalpies of branched-chain aliphatic and alkyl aromatic compounds at T = 298.15 K

    International Nuclear Information System (INIS)

    Varfolomeev, Mikhail A.; Novikov, Vladimir B.; Nagrimanov, Ruslan N.; Solomonov, Boris N.

    2015-01-01

    Highlights: • Solution enthalpies of 18 branching-chain alkyl aromatic and aliphatic compounds in cyclohexane were measured. • Group contributions to the enthalpy of solvation due to branching and substitution in carbon chain were evaluated. • Modified solution calorimetry based approach for determination of vaporization/sublimation enthalpies was proposed. • This approach provides vaporization/sublimation enthalpies directly at T = 298.15 K. • Vaporization/sublimation enthalpies of 35 branched-chain alkyl aromatic and aliphatic compounds were determined. - Abstract: The enthalpies of solution, solvation and vaporization/sublimation are interrelated values combined in the simplest thermodynamic circle. Hence, experimental determination of vaporization/sublimation enthalpy can be substituted by experimentally simpler determination of solution enthalpy when solvation enthalpy is known. Previously it was found that solvation enthalpies of a wide range of unbranched aliphatic and aromatic solutes in saturated hydrocarbons are in good linear correlation with their molar refraction values. This allows to estimate the vaporization/sublimation enthalpy of any unbranched organic compound from its solution enthalpy in saturated hydrocarbon and molar refraction. In the present work this approach was modified for determination of vaporization/sublimation enthalpy of branched-chain alkyl aromatic and aliphatic compounds. Group contributions to the enthalpy of solvation due to the branching of carbon chain were evaluated. Enthalpies of solution at infinite dilution of 18 branched-chain aliphatic and alkyl aromatic compounds were measured at T = 298.15 K. Vaporization/sublimation enthalpies for 35 branched aliphatic and alkyl aromatic compounds were determined by using modified solution calorimetry approach. These values are in good agreement with available literature data on vaporization/sublimation enthalpies obtained by conventional methods.

  14. Standard enthalpies of formation of 2-aminobenzothiazoles in the crystalline phase by rotating-bomb combustion calorimetry

    International Nuclear Information System (INIS)

    Camarillo, E. Adriana; Mentado, Juan; Flores, Henoc; Hernández-Pérez, Julio M.

    2014-01-01

    Highlights: • Rotating bomb calorimeter was used for combustion experiments. • Benzothiazole derivatives were studied by combustion experiments. • The standard molar enthalpies of combustion in solid phase were determined. • The enthalpies of formation in the solid phase were derived. • Experimental and predicted values were used to determine gaseous formation enthalpies. - Abstract: The standard molar enthalpies of combustion of 2-aminobenzothiazole (2AB), 2-amino-4-methyl-benzothiazole (2A4MB), and 2-amino-6-methyl-benzothiazole (2A6MB) were determined in the crystalline phase at T = 298.15 K using a rotating-bomb combustion calorimeter. The molar energies of combustion of these compounds were found to be: (−4273.6 ± 0.9), (−4896.9 ± 1.1), and (−4906.9 ± 1.2) kJ · mol −1 , respectively. From these values, the corresponding standard molar enthalpies of formation in the solid phase were obtained as: (59.55 ± 1.28), (2.71 ± 1.50), and (13.53 ± 1.53) kJ · mol −1 , respectively. The enthalpies of formation in the gas phase were determined using the experimental enthalpies of formation in the solid phase and predicted values of the enthalpies of sublimation. Additionally, the enthalpies of formation in the gas phase were calculated by means of the Gausian-4 theory, using several gas-phase working reactions, and were compared with those found using the predicted enthalpies of sublimation

  15. The GEOVIDE cruise in May–June 2014 reveals an intense Meridional Overturning Circulation over a cold and fresh subpolar North Atlantic

    Directory of Open Access Journals (Sweden)

    P. Zunino

    2017-11-01

    Full Text Available The GEOVIDE cruise was carried out in the subpolar North Atlantic (SPNA along the OVIDE section and across the Labrador Sea in May–June 2014. It was planned to clarify the distribution of the trace elements and their isotopes in the SPNA as part of the GEOTRACES international program. This paper focuses on the state of the circulation and distribution of thermohaline properties during the cruise. In terms of circulation, the comparison with the 2002–2012 mean state shows a more intense Irminger Current and also a weaker North Atlantic Current, with a transfer of volume transport from its northern to its central branch. However, those anomalies are compatible with the variability already observed along the OVIDE section in the 2000s. In terms of properties, the surface waters of the eastern SPNA were much colder and fresher than the averages over 2002–2012. In spite of negative temperature anomalies in the surface waters, the heat transport across the OVIDE section estimated at 0.56 ± 0.06 PW was the largest measured since 2002. This relatively large value is related to the relatively strong Meridional Overturning Circulation measured across the OVIDE section during GEOVIDE (18.7 ± 3.0 Sv. By analyzing the air–sea heat and freshwater fluxes over the eastern SPNA in relation to the heat and freshwater content changes observed during 2013 and 2014, we concluded that on a short timescale these changes were mainly driven by air–sea heat and freshwater fluxes rather than by ocean circulation.

  16. The GEOVIDE cruise in May-June 2014 reveals an intense Meridional Overturning Circulation over a cold and fresh subpolar North Atlantic

    Science.gov (United States)

    Zunino, Patricia; Lherminier, Pascale; Mercier, Herlé; Daniault, Nathalie; García-Ibáñez, Maribel I.; Pérez, Fiz F.

    2017-11-01

    The GEOVIDE cruise was carried out in the subpolar North Atlantic (SPNA) along the OVIDE section and across the Labrador Sea in May-June 2014. It was planned to clarify the distribution of the trace elements and their isotopes in the SPNA as part of the GEOTRACES international program. This paper focuses on the state of the circulation and distribution of thermohaline properties during the cruise. In terms of circulation, the comparison with the 2002-2012 mean state shows a more intense Irminger Current and also a weaker North Atlantic Current, with a transfer of volume transport from its northern to its central branch. However, those anomalies are compatible with the variability already observed along the OVIDE section in the 2000s. In terms of properties, the surface waters of the eastern SPNA were much colder and fresher than the averages over 2002-2012. In spite of negative temperature anomalies in the surface waters, the heat transport across the OVIDE section estimated at 0.56 ± 0.06 PW was the largest measured since 2002. This relatively large value is related to the relatively strong Meridional Overturning Circulation measured across the OVIDE section during GEOVIDE (18.7 ± 3.0 Sv). By analyzing the air-sea heat and freshwater fluxes over the eastern SPNA in relation to the heat and freshwater content changes observed during 2013 and 2014, we concluded that on a short timescale these changes were mainly driven by air-sea heat and freshwater fluxes rather than by ocean circulation.

  17. Enthalpies of formation of selected Co{sub 2}YZ Heusler compounds

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Ming, E-mail: myin1@hawk.iit.edu; Chen, Song; Nash, Philip

    2013-11-15

    Highlights: •Enthalpies of formation of selected Co{sub 2}YZ were measured by drop calorimeters. •Enthalpy decreases as the Z element approaches the top right corner of the periodic table. •For the Y element, enthalpy increases on increasing the number of d electrons. •Result of L2{sub 1} structured compounds agrees with first principles data. •Lattice parameters and related phase relationships were consistent with literature data. -- Abstract: Standard enthalpies of formation at 298 K of selected ternary Co{sub 2}-based Heusler compounds Co{sub 2}YZ (Y = Fe, Hf, Mn, Ti, V, Zr; Z = Al, Ga, In, Si, Ge, Sn) were measured by high temperature direct synthesis calorimetry. The measured enthalpies of formation (in kJ/mole of atoms) of the L2{sub 1} compounds are: Co{sub 2}FeGa (−25.8 ± 2.6); Co{sub 2}FeSi (−38.4 ± 2.2); Co{sub 2}FeGe (−11.6 ± 2.1); Co{sub 2}MnGa (−30.1 ± 2.3); Co{sub 2}MnSi (−42.4 ± 1.2); Co{sub 2}MnGe (−31.6 ± 3.0); Co{sub 2}MnSn (−15.6 ± 2.8); Co{sub 2}TiAl (−55.0 ± 3.7); Co{sub 2}TiGa (−54.2 ± 2.6); Co{sub 2}TiSi (−61.4 ± 1.7); Co{sub 2}TiGe (−59.3 ± 3.8); Co{sub 2}TiSn (−38.4 ± 2.0); Co{sub 2}VGa (−28.4 ± 1.1) and for the B2 compounds: Co{sub 2}FeAl (−22.5 ± 2.5), Co{sub 2}MnAl (−27.6 ± 2.7). Values are compared with those from first principles calculation when available and the extended semi-empirical model of Miedema. Trends in enthalpy of formation with element atomic number are discussed. Lattice parameters of the compounds with L2{sub 1} structure are determined by X-ray diffraction analysis.

  18. Prediction of failure enthalpy and reliability of irradiated fuel rod under reactivity-initiated accidents by means of statistical approach

    International Nuclear Information System (INIS)

    Nam, Cheol; Choi, Byeong Kwon; Jeong, Yong Hwan; Jung, Youn Ho

    2001-01-01

    During the last decade, the failure behavior of high-burnup fuel rods under RIA has been an extensive concern since observations of fuel rod failures at low enthalpy. Of great importance is placed on failure prediction of fuel rod in the point of licensing criteria and safety in extending burnup achievement. To address the issue, a statistics-based methodology is introduced to predict failure probability of irradiated fuel rods. Based on RIA simulation results in literature, a failure enthalpy correlation for irradiated fuel rod is constructed as a function of oxide thickness, fuel burnup, and pulse width. From the failure enthalpy correlation, a single damage parameter, equivalent enthalpy, is defined to reflect the effects of the three primary factors as well as peak fuel enthalpy. Moreover, the failure distribution function with equivalent enthalpy is derived, applying a two-parameter Weibull statistical model. Using these equations, the sensitivity analysis is carried out to estimate the effects of burnup, corrosion, peak fuel enthalpy, pulse width and cladding materials used

  19. Chaotic variability of the meridional overturning circulation on subannual to interannual timescales

    Directory of Open Access Journals (Sweden)

    J. J.-M. Hirschi

    2013-09-01

    Full Text Available Observations and numerical simulations have shown that the meridional overturning circulation (MOC exhibits substantial variability on sub- to interannual timescales. This variability is not fully understood. In particular it is not known what fraction of the MOC variability is caused by processes such as mesoscale ocean eddies and waves which are ubiquitous in the ocean. Here we analyse twin experiments performed with a global ocean model at eddying (1/4° and non-eddying (1° resolutions. The twin experiments are forced with the same surface fluxes for the 1958 to 2001 period but start from different initial conditions. Our results show that on subannual to interannual timescales a large fraction of MOC variability directly reflects variability in the surface forcing. Nevertheless, in the eddy-permitting case there is an initial-condition-dependent MOC variability (hereinafter referred to as "chaotic" variability of several Sv (1Sv = 106 m3 s−1 in the Atlantic and the Indo-Pacific. In the Atlantic the chaotic MOC variability represents up to 30% of the total variability at the depths where the maximum MOC occurs. In comparison the chaotic MOC variability is only 5–10% in the non-eddying case. The surface forcing being almost identical in the twin experiments suggests that mesoscale ocean eddies are the most likely cause for the increased chaotic MOC variability in the eddying case. The exact formation time of eddies is determined by the initial conditions which are different in the two model passes, and as a consequence the mesoscale eddy field is decorrelated in the twin experiments. In regions where eddy activity is high in the eddy-permitting model, the correlation of sea surface height variability in the twin runs is close to zero. In the non-eddying case in contrast, we find high correlations (0.9 or higher over most regions. Looking at the sub- and interannual MOC components separately reveals that most of the chaotic MOC variability

  20. The importance of deep, basinwide measurements in optimized Atlantic Meridional Overturning Circulation observing arrays

    Science.gov (United States)

    McCarthy, G. D.; Menary, M. B.; Mecking, J. V.; Moat, B. I.; Johns, W. E.; Andrews, M. B.; Rayner, D.; Smeed, D. A.

    2017-03-01

    The Atlantic Meridional Overturning Circulation (AMOC) is a key process in the global redistribution of heat. The AMOC is defined as the maximum of the overturning stream function, which typically occurs near 30°N in the North Atlantic. The RAPID mooring array has provided full-depth, basinwide, continuous estimates of this quantity since 2004. Motivated by both the need to deliver near real-time data and optimization of the array to reduce costs, we consider alternative configurations of the mooring array. Results suggest that the variability observed since 2004 could be reproduced by a single tall mooring on the western boundary and a mooring to 1500 m on the eastern boundary. We consider the potential future evolution of the AMOC in two generations of the Hadley Centre climate models and a suite of additional CMIP5 models. The modeling studies show that deep, basinwide measurements are essential to capture correctly the future decline of the AMOC. We conclude that, while a reduced array could be useful for estimates of the AMOC on subseasonal to decadal time scales as part of a near real-time data delivery system, extreme caution must be applied to avoid the potential misinterpretation or absence of a climate time scale AMOC decline that is a key motivation for the maintenance of these observations.Plain Language SummaryThe Atlantic Overturning Circulation is a system of ocean currents that carries heat northwards in the Atlantic. This heat is crucial to maintaining the mild climate of northwest Europe. The Overturning Circulation is predicted to slow in future in response to man-made climate change. The RAPID program is designed to measure the Overturning Circulation using a number of fixed point observations spanning the Atlantic between the Canary Islands and the Bahamas. We look at whether we could reduce the number of these fixed point observations to continue to get accurate estimates of the overturning strength but for less cost. We conclude that

  1. Meltwater routing and the Atlantic meridional overturning circulation: A Gulf of Mexico perspective

    Science.gov (United States)

    Flower, B. P.; Williams, C.; Randle, N.; Hastings, D. W.

    2008-12-01

    Routing of low-salinity meltwater from the Laurentide Ice Sheet (LIS) into the North Atlantic via eastern outlets (e.g., St. Lawrence and Hudson River systems) and northern outlets (e.g., Hudson Bay and Arctic Ocean) is thought to have reduced Atlantic meridional overturning circulation (AMOC) and thereby triggered rapid regional to global climate change during the last glacial cycle. In contrast, southward meltwater flow to the Gulf of Mexico is generally thought to allow enhanced AMOC and warmer climates in the North Atlantic region. Situated at the outlet of the Mississippi River system, Orca Basin is ideally located to record meltwater input from the LIS. Orca Basin core MD02-2550 collected by the R/V Marion Dufresne in 2002 on IMAGES cruise VIII allows sub-centennial-scale records of Mg/Ca sea-surface temperature (SST) and δ18Oseawater back to ca. 23.9 ka. Accumulation rates average about 40 cm/k.y. Our current data extend from ca. 16.5-7 ka, with age control provided by 40 AMS radiocarbon dates (nearly all in stratigraphic order; calibrated using Calib 5.0.2). We use paired Mg/Ca and oxygen isotope data on Globigerinoides ruber to isolate changes in the oxygen isotopic composition of seawater. Four major episodic δ18O decreases of more than 2 per mil indicate substantial LIS meltwater input. Intervals of major meltwater discharge to the Gulf of Mexico do not appear to match known pulses of global sea level increase. However, abrupt reductions in southward meltwater input to the Gulf of Mexico seem to correlate with abrupt coolings in the North Atlantic region (e.g., Younger Dryas, Intra-Allerod cold period, and Oldest Dryas). In particular, a 3.5 per mil δ18O increase centered at 10,970 radiocarbon years B.P. (the "cessation event") appears to coincide with the onset of the Younger Dryas in European lakes and with Δ14C evidence from Cariaco Basin for AMOC reduction. Furthermore, recent results with the NCAR Community Climate System model (CCSM3) indicate

  2. Dissolution enthalpies of L-proline and its interactions with methanol, 2-propanol, ethylene glycol, and glycerin in aqueous solution at 298.15 K

    Science.gov (United States)

    Korolev, V. P.; Antonova, O. A.; Smirnova, N. L.

    2010-12-01

    The dissolution enthalpies of L-proline in mixtures of water with methanol, 2-propanol, ethylene glycol, and glycerin were measured calorimetrically at 298.15 K. The enthalpy coefficients of the interaction of proline with alcohols in aqueous solutions were determined. The enthalpy coefficients of the pair interaction of proline and glycine with alcohols were shown to be directly proportional.

  3. Free Energy, Enthalpy and Entropy from Implicit Solvent End-Point Simulations

    Science.gov (United States)

    Fogolari, Federico; Corazza, Alessandra; Esposito, Gennaro

    2018-01-01

    Free energy is the key quantity to describe the thermodynamics of biological systems. In this perspective we consider the calculation of free energy, enthalpy and entropy from end-point molecular dynamics simulations. Since the enthalpy may be calculated as the ensemble average over equilibrated simulation snapshots the difficulties related to free energy calculation are ultimately related to the calculation of the entropy of the system and in particular of the solvent entropy. In the last two decades implicit solvent models have been used to circumvent the problem and to take into account solvent entropy implicitly in the solvation terms. More recently outstanding advancement in both implicit solvent models and in entropy calculations are making the goal of free energy estimation from end-point simulations more feasible than ever before. We review briefly the basic theory and discuss the advancements in light of practical applications. PMID:29473043

  4. The enthalpy of solid scandium in the temperature range 406 - 1812 K

    International Nuclear Information System (INIS)

    Lyapunov, K.M.; Baginskij, A.V.; Stankus, S.V.

    2001-01-01

    Enthalpy of pure scandium was measured on massive calorimeter in the range from 406 to 1812 K by mixing method. The enthalpy of face centered close cubic lattice - body centered cubic lattice transformation is equal to ΔH t 4068 J/mol. Obtained value within the limits of error is compatible with the results given earlier (4009 J/mol). The dependence of the middle specific heat of scandium C p (T) on the temperature was shown in correlation with the results of other works. The results of the conducted experiments reinforce the conclusion made earlier about an absence (or a little) in the decomposition of an anharmonic component of the oscillation specific heat of scandium C p a (T) members proportional to the first or the second degrees of temperature [ru

  5. Air to air fixed plate enthalpy heat exchanger, performance variation and energy analysis

    Energy Technology Data Exchange (ETDEWEB)

    Nasif, Mohammad Shakir [Universiti Teknologi Petronas, Bandar Seri Iskandar (Malaysia); Alwaked, Rafat [Prince Mohammad Bin Fahd University, Al Khobar (Saudi Arabia); Behnia, Masud [University of Sydney, Sydney (Australia); Morrison, Graham [The University of New South Wales, Sydney (Australia)

    2013-11-15

    The thermal performance of a Z shape enthalpy heat exchanger utilising 70 gsm Kraft paper as the heat and moisture transfer surface has been investigated. Effects of different inlet air humidity ratio conditions on the heat exchanger effectiveness and on the energy recovered by the heat exchanger have been the main focus of this investigation. A typical air conditioning cooling coil which incorporates an enthalpy heat exchanger has been modelled for tropical climate. Under test conditions, results have shown that latent effectiveness and the moisture resistance coefficient have strong dependency on the inlet air humidity ratio. Moreover, the latent effectiveness has been found to be strongly dependent on the moisture resistance coefficient rather than the convective mass transfer coefficient. Finally, annual energy analysis for Singapore weather conditions have also shown that energy recovered under variable inlet air conditions is 15% less than that recovered under constant inlet air conditions for the same heat exchanger.

  6. Free Energy, Enthalpy and Entropy from Implicit Solvent End-Point Simulations

    Directory of Open Access Journals (Sweden)

    Federico Fogolari

    2018-02-01

    Full Text Available Free energy is the key quantity to describe the thermodynamics of biological systems. In this perspective we consider the calculation of free energy, enthalpy and entropy from end-point molecular dynamics simulations. Since the enthalpy may be calculated as the ensemble average over equilibrated simulation snapshots the difficulties related to free energy calculation are ultimately related to the calculation of the entropy of the system and in particular of the solvent entropy. In the last two decades implicit solvent models have been used to circumvent the problem and to take into account solvent entropy implicitly in the solvation terms. More recently outstanding advancement in both implicit solvent models and in entropy calculations are making the goal of free energy estimation from end-point simulations more feasible than ever before. We review briefly the basic theory and discuss the advancements in light of practical applications.

  7. Enthalpy-entropy compensation and the isokinetic temperature in enzyme catalysis.

    Science.gov (United States)

    Cornish-Bowden, Athel

    2017-12-01

    Enthalpy-entropy compensation supposes that differences in activation enthalpy ΔH++ for different reactions (or, typically in biochemistry, the same reaction catalysed by enzymes obtained from different species) may be compensated for by differences in activation entropy ΔS++. At the isokinetic temperature the compensation is exact, so that all samples have the same activity. These ideas have been controversial for several decades, but examples are still frequently reported as evidence of a real phenomenon, nearly all of the reports ignoring or discounting the possibility of a statistical artefact. Even for measurements in pure chemistry artefacts occur often, and they are almost inescapable in enzyme kinetics and other fields that involve biological macromolecules, on account of limited stability and the fact that kinetic equations are normally valid only over a restricted range of temperature. Here I review the current status and correct an error in a recent book chapter.

  8. The influence of facies heterogeneity on the doublet performance in low-enthalpy geothermal sedimentary reservoirs

    DEFF Research Database (Denmark)

    Crooijmans, R. A.; Willems, C. J L; Nick, Hamid

    2016-01-01

    A three-dimensional model is used to study the influence of facies heterogeneity on energy production under different operational conditions of low-enthalpy geothermal doublet systems. Process-based facies modelling is utilised for the Nieuwerkerk sedimentary formation in the West Netherlands Basin...... and the energy recovery rate for different discharge rates and the production temperature (Tmin) above which the doublet is working. With respect to the results, we propose a design model to estimate the life time and energy recovery rate of the geothermal doublet. The life time is estimated as a function of N...... errors in predicting the life time of low-enthalpy geothermal systems for N/G values below 70%....

  9. Generalized enthalpy model of a high-pressure shift freezing process

    KAUST Repository

    Smith, N. A. S.

    2012-05-02

    High-pressure freezing processes are a novel emerging technology in food processing, offering significant improvements to the quality of frozen foods. To be able to simulate plateau times and thermal history under different conditions, in this work, we present a generalized enthalpy model of the high-pressure shift freezing process. The model includes the effects of pressure on conservation of enthalpy and incorporates the freezing point depression of non-dilute food samples. In addition, the significant heat-transfer effects of convection in the pressurizing medium are accounted for by solving the two-dimensional Navier-Stokes equations. We run the model for several numerical tests where the food sample is agar gel, and find good agreement with experimental data from the literature. © 2012 The Royal Society.

  10. Electrical resistivities and solvation enthalpies for solutions of salts in liquid alkali metals

    International Nuclear Information System (INIS)

    Hubberstey, P.; Dadd, A.T.

    1982-01-01

    An empirical correlation is shown to exist between the resistivity coefficients drho/dc for solutes in liquid alkali metals and the corresponding solvation enthalpies Usub(solvn) of the neutral gaseous solute species. Qualitative arguments based on an electrostatic solvation model in which the negative solute atom is surrounded by a solvation sphere of positive solvent ion cores are used to show that both parameters are dependent on the charge density of the solute atom and hence on the extent of charge transfer from solvent to solute. Thus as the charge density of the solute increases, the solvation enthalpy increases regularly and the resistivity coefficients pass through a maximum to give the observed approximately parabolic drho/dc versus Usub(solvn) relationship. (Auth.)

  11. Free Energy, Enthalpy and Entropy from Implicit Solvent End-Point Simulations.

    Science.gov (United States)

    Fogolari, Federico; Corazza, Alessandra; Esposito, Gennaro

    2018-01-01

    Free energy is the key quantity to describe the thermodynamics of biological systems. In this perspective we consider the calculation of free energy, enthalpy and entropy from end-point molecular dynamics simulations. Since the enthalpy may be calculated as the ensemble average over equilibrated simulation snapshots the difficulties related to free energy calculation are ultimately related to the calculation of the entropy of the system and in particular of the solvent entropy. In the last two decades implicit solvent models have been used to circumvent the problem and to take into account solvent entropy implicitly in the solvation terms. More recently outstanding advancement in both implicit solvent models and in entropy calculations are making the goal of free energy estimation from end-point simulations more feasible than ever before. We review briefly the basic theory and discuss the advancements in light of practical applications.

  12. Enthalpy of solution of biuret in various aqueous electrolyte solutions and in an urea solution

    Energy Technology Data Exchange (ETDEWEB)

    Nishimura, Hisashi; Murakami, Sachio (Osaka City Univ. (Japan))

    1989-06-30

    Enthalpies of biuret which is simplest amido acid and does not have hydrophobic group, in various aqueous solutions and in urea solution were measured at 298.15K to clarify the influence of salt on polymer conformal changes of organism or structure and functions of membrane. The isoperibol calorimeter where the quartz thermometer was used as the thermal sensor, was used in the measurement. The performance of this calorimeter was tested by comparing measurements with values in references. From the analysis of enthalpies of biuret solutions, following results of solute-solute-solvent interactions could be obtained: the rate where biuret destroys water structure is smaller in salt solutions than in aqueous solutions and the tendency depends on the ion size; ion-water interaction weakens owing to the ion-biuret interaction in salt solution of biuret; and water molecules are made free. 25 refs., 4 figs., 5 tabs.

  13. Accurate Computed Enthalpies of Spin Crossover in Iron and Cobalt Complexes

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta; Cirera, J

    2009-01-01

    Despite their importance in many chemical processes, the relative energies of spin states of transition metal complexes have so far been haunted by large computational errors. By the use of six functionals, B3LYP, BP86, TPSS, TPSSh, M06L, and M06L, this work studies nine complexes (seven with iron...... effects of first-row transition metal systems. Furthermore, it is shown that given an experimental structure of an iron complex, TPSSh can predict the electronic state corresponding to that experimental structure. We recommend this functional as current state-of-the-art for studying spin crossover...... and two with cobalt) for which experimental enthalpies of spin crossover are available. It is shown that such enthalpies can be used as quantitative benchmarks of a functional's ability to balance electron correlation in both the involved states. TPSSh achieves an unprecedented mean absolute error...

  14. Evaluation of enthalpy of interfacial reactions from temperature dependency of interfacial equilibrium

    International Nuclear Information System (INIS)

    Kallay, Nikola; Cop, Ana

    2005-01-01

    Temperature dependency of equilibrium at metal oxide-aqueous electrolyte solution interface was analyzed by numerical simulation. Derivations of inner surface potential with respect to temperature were performed at constant values of several different parameters. When surface charge density in inner plane was kept constant the reasonable results were obtained, i.e. the electrostatic contribution to enthalpy of protonation of amphotheric surface sites was found to be positive in the pH region below the point of zero potential and negative above this point. All other examined possibilities produced opposite results. Derivation of empirical interfacial equilibrium constant at constant surface potential indicated that electrostatic effect on protonation entropy is negligible and that electrostatic contributions to reaction Gibbs energy and enthalpy are equal and directly related to the surface potential in the inner plane

  15. Binding the Mammalian High Mobility Group Protein AT-hook 2 to AT-Rich Deoxyoligonucleotides: Enthalpy-Entropy Compensation

    OpenAIRE

    Joynt, Suzanne; Morillo, Victor; Leng, Fenfei

    2009-01-01

    HMGA2 is a DNA minor-groove binding protein. We previously demonstrated that HMGA2 binds to AT-rich DNA with very high binding affinity where the binding of HMGA2 to poly(dA-dT)2 is enthalpy-driven and to poly(dA)poly(dT) is entropy-driven. This is a typical example of enthalpy-entropy compensation. To further study enthalpy-entropy compensation of HMGA2, we used isothermal-titration-calorimetry to examine the interactions of HMGA2 with two AT-rich DNA hairpins: 5′-CCAAAAAAAAAAAAAAAGCCCCCGCTT...

  16. A comparison of pathway-independent and pathway-dependent methods in the calculation of conformational free enthalpy differences.

    OpenAIRE

    Lin Zhixiong; van Gunsteren Wilfred F

    2015-01-01

    The multistep umbrella sampling method, which belongs to pathway‐dependent methods to calculate conformational free enthalpy differences, is used to calculate the free enthalpy difference between a right‐handed 2.710/12‐helix and a left‐handed 314‐helix of a hexa‐β‐peptide in methanol solution. The same conformational free enthalpy difference was previously investigated using pathway‐independent methods such as direct counting and enveloping distribution sampling. Our results show that the pa...

  17. Enthalpy Distributions of Arc Jet Flow Based on Measured Laser Induced Fluorescence, Heat Flux and Stagnation Pressure Distributions

    Science.gov (United States)

    Suess, Leonard E.; Milhoan, James D.; Oelke, Lance; Godfrey, Dennis; Larin, Maksim Y.; Scott, Carl D.; Grinstead, Jay H.; DelPapa, Steven

    2011-01-01

    The centerline total enthalpy of arc jet flow is determined using laser induced fluorescence of oxygen and nitrogen atoms. Each component of the energy, kinetic, thermal, and chemical can be determined from LIF measurements. Additionally, enthalpy distributions are inferred from heat flux and pressure probe distribution measurements using an engineering formula. Average enthalpies are determined by integration over the radius of the jet flow, assuming constant mass flux and a mass flux distribution estimated from computational fluid dynamics calculations at similar arc jet conditions. The trends show favorable agreement, but there is an uncertainty that relates to the multiple individual measurements and assumptions inherent in LIF measurements.

  18. Excess enthalpies of the ternary mixtures: {tetrahydrofuran + 3-methylpentane + (octane or decane)} at the temperature 298.15 K

    International Nuclear Information System (INIS)

    Wang Zhaohui; Benson, George C.; Lu, Benjamin C.-Y.

    2003-01-01

    Measurements of excess molar enthalpies at the temperature 298.15 K in a flow microcalorimeter, are reported for the two ternary mixtures {X 1 C 4 H 8 O + X 2 CH 3 CH 2 CH(CH 3 )CH 2 CH 3 + (1-X 1 -X 2 )CH 3 (CH 2 ) v-2 CH 3 } with v=8 and 10. Smooth representations of the results are described and used to construct constant-enthalpy contours on Roozeboom diagrams. It is shown that useful estimates of the ternary enthalpies can be obtained from the Liebermann-Fried model, using only the physical properties of the components and their binary mixtures

  19. "What Controls the Structure and Stability of the Ocean Meridional Overturning Circulation: Implications for Abrupt Climate Change?"

    Energy Technology Data Exchange (ETDEWEB)

    Fedorov, Alexey [Yale University

    2013-11-23

    The central goal of this research project is to understand the properties of the ocean meridional overturning circulation (MOC) – a topic critical for understanding climate variability and stability on a variety of timescales (from decadal to centennial and longer). Specifically, we have explored various factors that control the MOC stability and decadal variability in the Atlantic and the ocean thermal structure in general, including the possibility abrupt climate change. We have also continued efforts on improving the performance of coupled ocean-atmosphere GCMs.

  20. De Indios “Bárbaros” a Vasallos en la Frontera Meridional Chilena Durante el Reformismo Borbónico.

    OpenAIRE

    Chauca García, Jorge

    2017-01-01

    Con la presente Tesis Doctoral abordamos críticamente la visión ilustrada del indígena de la frontera meridional chilena como marco geográfico y la centuria de la Ilustración como coordenada temporal, especialmente su segunda mitad. Un análisis de sus tres familias básicas que no contempla por razones cronológicas a los picunches o gentes del norte, pero sí a los mapuches –gente de la tierra–, huilliches –gente...

  1. Tuning facial-meridional isomerisation in monometallic nine-co-ordinate lanthanide complexes with unsymmetrical tridentate ligands.

    Science.gov (United States)

    Le Borgne, Thierry; Altmann, Peter; André, Nicolas; Bünzli, Jean-Claude G; Bernardinelli, Gérald; Morgantini, Pierre-Yves; Weber, Jacques; Piguet, Claude

    2004-03-07

    The unsymmetrical tridentate benzimidazole-pyridine-carboxamide units in ligands L1-L4 react with trivalent lanthanides, Ln(III), to give the nine-co-ordinate triple-helical complexes [Ln(Li)3]3+ (i = 1-4) existing as mixtures of C3-symmetrical facial and C1-symmetrical meridional isomers. Although the beta13 formation constants are 3-4 orders of magnitude smaller for these complexes than those found for the D3-symmetrical analogues [Ln(Li)3]3+ (i = 5-6) with symmetrical ligands, their formation at the millimolar scale is quantitative and the emission quantum yield of [Eu(L2)3]3+ is significantly larger. The fac-[Ln(Li)3]3+ mer-[Ln(Li)3]3+ (i = 1-4) isomerisation process in acetonitrile is slow enough for Ln = Lu(III) to be quantified by 1H NMR below room temperature. The separation of enthalpic and entropic contributions shows that the distribution of the facial and meridional isomers can be tuned by the judicious peripheral substitution of the ligands affecting the interstrand interactions. Molecular mechanics (MM) calculations suggest that one supplementary interstrand pi-stacking interaction stabilises the meridional isomers, while the facial isomers benefit from more favourable electrostatic contributions. As a result of the mixture of facial and meridional isomers in solution, we were unable to obtain single crystals of 1:3 complexes, but the X-ray crystal structures of their nine-co-ordinate precursors [Eu(L1)2(CF3SO3)2(H2O)](CF3SO3)(C3H5N)2(H2O) (6, C45H54EuF9N10O13S3, monoclinic, P2(1)/c, Z = 4) and [Eu(L4)2(CF3SO3)2(H2O)](CF3SO3)(C4H4O)(1.5) (7, C51H66EuF9N8O(15.5)S3, triclinic, P1, Z = 2) provide crucial structural information on the binding mode of the unsymmetrical tridentate ligands.

  2. Enthalpy of phase transition and prediction of phase Equilibria in systems of glycols and glycol ethers

    OpenAIRE

    Esina, Zoya; Miroshnikov, Aleksandr; Korchuganova, Margarita

    2014-01-01

    The PCEAS model was used to study the liquid-solid and liquid-vapor phase transitions at constant pressure in systems containing glycols and glycol ethers. This method is based on minimizing the excess Gibbs energy over the solvation parameter, which takes into account the processes of association of molecules in various phases. To compute the diagrams, the data on enthalpy and phase transition temperatures of pure components are required, while the information about the interactions in the b...

  3. Standard enthalpies of formation of selected Rh{sub 2}YZ Heusler compounds

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Ming, E-mail: myin1@hawk.iit.edu; Nash, Philip

    2015-11-25

    The standard enthalpies of formation (Δ{sub f}H°) of selected ternary Rh-based Rh{sub 2}YZ (Y = Cu, Fe, Mn, Ni, Ru, Ti, V; Z = Al, Ga, In, Si, Ge, Sn) compounds were measured using high temperature direct reaction calorimetry. The measured standard enthalpies of formation (in kJ/mol of atoms) are, for the Heusler compound Rh{sub 2}MnSn (−40.1 ± 3.6), for the B2-structured compounds: Rh{sub 2}FeAl (−48.5 ± 2.9); Rh{sub 2}MnAl (−72.4 ± 2.7); Rh{sub 2}MnGa (−55.3 ± 2.0); Rh{sub 2}MnIn (−35.3 ± 1.9), for the tetragonal compounds: Rh{sub 2}FeSn (−28.9 ± 1.3); Rh{sub 2}TiAl (−97.6 ± 2.2); Rh{sub 2}TiGa (−79.0 ± 1.8); Rh{sub 2}TiSn (−74.7 ± 3.1). Values are compared with those from first principles calculations in published papers and the Open Quantum Materials Database (OQMD). Lattice parameters of these compounds are determined using X-ray diffraction analysis (XRD). Microstructures were characterized using scanning electron microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). - Highlights: • Standard enthalpies of formation of Rh{sub 2}YZ were measured using a drop calorimeter. • Measured enthalpies agree with first principles data in general. • Lattice parameters and related phase relationships were consistent with literature data. • Rh{sub 2}TiSn of tI8 structure were reported for the first time.

  4. Improved simplified scheme of atom equivalents to calculate enthalpies of formation of alkyl radicals

    International Nuclear Information System (INIS)

    Castro, Eduardo A.

    2002-01-01

    An improved simplified method of atom equivalents is applied to the calculation of enthalpies of formation of several alkyl radicals. Some statistical mechanics and thermodynamic corrections are added to compare theoretical values with available experimental data. The estimation is quite satisfactory and the average error is similar to current experimental uncertainties, thus providing a direct and simple procedure for this sort of calculation when experimental results are unavailable or/and as an independent check when experimental data are in doubt. (Author) [es

  5. Dependence of the enthalpy of the direct martensitic transformation in titanium nickelide on the stress

    Science.gov (United States)

    Egorov, S. A.; Volkov, A. E.

    2017-02-01

    An original technique of differential thermal analysis for studying thermal properties of samples loaded with a tangential stress has been created. In a series of experiments studying the direct martensitic transformation B2 → B19' in titanium nickelide during cooling under constant stress, it has been found that the enthalpy of transformation linearly decreases with an increase in stress and, at a stress of 100 MPa, it is 30% less than that of the sample in a free state.

  6. Kinetic evidence of an apparent negative activation enthalpy in an organocatalytic process

    KAUST Repository

    Han, Xiao

    2013-08-30

    A combined kinetic and computational study on our tryptophan-based bifunctional thiourea catalyzed asymmetric Mannich reactions reveals an apparent negative activation enthalpy. The formation of the pre-transition state complex has been unambiguously confirmed and these observations provide an experimental support for the formation of multiple hydrogen bonding network between the substrates and the catalyst. Such interactions allow the creation of a binding cavity, a key factor to install high enantioselectivity.

  7. Dominant Alcohol-Protein Interaction via Hydration-Enabled Enthalpy-Driven Binding Mechanism.

    Science.gov (United States)

    Chong, Yuan; Kleinhammes, Alfred; Tang, Pei; Xu, Yan; Wu, Yue

    2015-04-30

    Water plays an important role in weak associations of small drug molecules with proteins. Intense focus has been on binding-induced structural changes in the water network surrounding protein binding sites, especially their contributions to binding thermodynamics. However, water is also tightly coupled to protein conformations and dynamics, and so far little is known about the influence of water-protein interactions on ligand binding. Alcohols are a type of low-affinity drugs, and it remains unclear how water affects alcohol-protein interactions. Here, we present alcohol adsorption isotherms under controlled protein hydration using in situ NMR detection. As functions of hydration level, Gibbs free energy, enthalpy, and entropy of binding were determined from the temperature dependence of isotherms. Two types of alcohol binding were found. The dominant type is low-affinity nonspecific binding, which is strongly dependent on temperature and the level of hydration. At low hydration levels, this nonspecific binding only occurs above a threshold of alcohol vapor pressure. An increased hydration level reduces this threshold, with it finally disappearing at a hydration level of h ≈ 0.2 (g water/g protein), gradually shifting alcohol binding from an entropy-driven to an enthalpy-driven process. Water at charged and polar groups on the protein surface was found to be particularly important in enabling this binding. Although further increase in hydration has smaller effects on the changes of binding enthalpy and entropy, it results in a significant negative change in Gibbs free energy due to unmatched enthalpy-entropy compensation. These results show the crucial role of water-protein interplay in alcohol binding.

  8. An evaluation of interferences in heat production from low enthalpy geothermal doublets systems

    DEFF Research Database (Denmark)

    Willems, Cees J. L.; Nick, Hamidreza M.; Weltje, Gert Jan

    2017-01-01

    Required distance between doublet systems in low enthalpy geothermal heat exploitation is often not fully elucidated. The required distance aims to prevent negative interference influencing the utilisation efficiency of doublet systems. Currently production licence areas are often issued based...... and minimal required production temperature. The results of this study can be used to minimize negative interference or optimise positive interference aiming at improving geothermal doublet deployment efficiency. (C) 2017 The Authors. Published by Elsevier Ltd....

  9. Investigating ultra high-enthalpy geothermal systems: a collaborative initiative to promote scientific opportunities

    Science.gov (United States)

    Elders, W. A.; Nielson, D.; Schiffman, P.; Schriener, A., Jr.

    2014-12-01

    Scientists, engineers, and policy makers gathered at a workshop in the San Bernardino Mountains of southern California in October 2013 to discuss the science and technology involved in developing high-enthalpy geothermal fields. A typical high-enthalpy geothermal well between 2000 and 3000 m deep produces a mixture of hot water and steam at 200-300 °C that can be used to generate about 5-10 MWe of electric power. The theme of the workshop was to explore the feasibility and economic potential of increasing the power output of geothermal wells by an order of magnitude by drilling deeper to reach much higher pressures and temperatures. Development of higher enthalpy geothermal systems for power production has obvious advantages; specifically higher temperatures yield higher power outputs per well so that fewer wells are needed, leading to smaller environmental footprints for a given size of power plant. Plans for resource assessment and drilling in such higher enthalpy areas are already underway in Iceland, New Zealand, and Japan. There is considerable potential for similar developments in other countries that already have a large production of electricity from geothermal steam, such as Mexico, the Philippines, Indonesia, Italy, and the USA. However drilling deeper involves technical and economic challenges. One approach to mitigating the cost issue is to form a consortium of industry, government and academia to share the costs and broaden the scope of investigation. An excellent example of such collaboration is the Iceland Deep Drilling Project (IDDP), which is investigating the economic feasibility of producing electricity from supercritical geothermal reservoirs, and this approach could serve as model for future developments elsewhere. A planning committee was formed to explore creating a similar initiative in the USA.

  10. Standard enthalpies of formation of selected Rh2YZ Heusler compounds

    International Nuclear Information System (INIS)

    Yin, Ming; Nash, Philip

    2015-01-01

    The standard enthalpies of formation (Δ f H°) of selected ternary Rh-based Rh 2 YZ (Y = Cu, Fe, Mn, Ni, Ru, Ti, V; Z = Al, Ga, In, Si, Ge, Sn) compounds were measured using high temperature direct reaction calorimetry. The measured standard enthalpies of formation (in kJ/mol of atoms) are, for the Heusler compound Rh 2 MnSn (−40.1 ± 3.6), for the B2-structured compounds: Rh 2 FeAl (−48.5 ± 2.9); Rh 2 MnAl (−72.4 ± 2.7); Rh 2 MnGa (−55.3 ± 2.0); Rh 2 MnIn (−35.3 ± 1.9), for the tetragonal compounds: Rh 2 FeSn (−28.9 ± 1.3); Rh 2 TiAl (−97.6 ± 2.2); Rh 2 TiGa (−79.0 ± 1.8); Rh 2 TiSn (−74.7 ± 3.1). Values are compared with those from first principles calculations in published papers and the Open Quantum Materials Database (OQMD). Lattice parameters of these compounds are determined using X-ray diffraction analysis (XRD). Microstructures were characterized using scanning electron microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). - Highlights: • Standard enthalpies of formation of Rh 2 YZ were measured using a drop calorimeter. • Measured enthalpies agree with first principles data in general. • Lattice parameters and related phase relationships were consistent with literature data. • Rh 2 TiSn of tI8 structure were reported for the first time.

  11. Energetic studies of urea derivatives: Standard molar enthalpy of formation of 3,4,4'-trichlorocarbanilide

    International Nuclear Information System (INIS)

    Ribeiro da Silva, Maria das Dores M.C.; Ribeiro da Silva, Manuel A.V.; Freitas, Vera L.S.; Roux, Maria Victoria; Jimenez, Pilar; Davalos, Juan Z.; Cabildo, Pilar; Claramunt, Rosa M.; Pinilla, Elena; Rosario Torres, M.; Elguero, Jose

    2010-01-01

    Thermochemical and thermophysical studies have been carried out for crystalline 3,4,4'-trichlorocarbanilide. The standard (p o = 0.1 MPa) molar enthalpy of formation, at T = 298.15 K, for the crystalline 3,4,4'-trichlorocarbanilide (TCC) was experimentally determined using rotating-bomb combustion calorimetry, as -(234.6 ± 8.3) kJ . mol -1 . The standard enthalpy of sublimation, at the reference temperature of 298.15 K, was measured by the vacuum drop microcalorimetric technique, using a High Temperature Calvet Microcalorimeter as (182.1 ± 1.7) kJ . mol -1 . These two thermochemical parameters yielded the standard molar enthalpy of formation of the studied compound, in the gaseous phase, at T = 298.15 K, as -(52.5 ± 8.5) kJ . mol -1 . This parameter was also calculated by computational thermochemistry at M05-2X/6-311++G** and B3LYP/6-311++G(3df, 2p) levels, with a deviation less than 4.5 kJ . mol -1 from experimental value. Moreover, the thermophysical study was made by differential scanning calorimetry, DSC, over the temperature interval between T = 263 K and its onset fusion temperature, T = (527.5 ± 0.4) K. A solid-solid phase transition was found at T = (428 ± 1) K, with the enthalpy of transition of (6.1 ± 0.1) kJ . mol -1 . The X-ray crystal structure of TCC was determined and the three-centred N-H...O=C hydrogen bonds present analyzed.

  12. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns

    2005-05-11

    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

  13. Outlook on principles for designing integrated and cascade use of low enthalpy geothermal energy in Albania

    International Nuclear Information System (INIS)

    Frasheri, Alfred

    2000-01-01

    In the countries of Western Europe, USA and Japan, the technologies of a new generation evolved to exploit high and low enthalpy geothermal sources and mineral waters. There are great experiences for modern complex exploitation of these resources, which increase natural wealth values, in European Community Countries. In Albania, rich in geothermal resources of low enthalpy and mineral waters, similar new technologies have been either partly developed or remain still untouched. Modern complex exploitation is very rare phenomena. Large numbers of geothermal energy of high and low enthalpy resources, a lot of mineral water sources and some CO 2 gas reservoirs represent the base for successfully application of modern technologies in Albania, to achieve economic effectively and success of complex exploitation. Actuality, there are many geothermal, hydrogeological, hydrochemical, biological and medical investigations and studies of thermal and mineral water resources carried out in Albania. Generally, these investigations and studies are separated each from the other. Their information and data will serve for studies and evaluations in Albania regional scale. These studies and evaluations are necessary to well know in regional plane the thermal and mineral water resources potential and geothermal market of the Albania. According to results of these new studies, the evaluation for the perspective level of the best areas in country will be necessary. After the evaluation is possible to start investments in these areas. These investments will be profitable in a short period of time. Integrated and cascade use of geothermal energy of low enthalpy it is important condition for profitable investment. In Albania, there are several geothermal energy sources that can be used. Such geothermal energy sources are natural thermal water springs and deep wells with a temperature of up to 65,5 o C. Deep abandoned oil wells can be used as 'Vertical Earth Heat Probe'. The integrated and

  14. Dominant Alcohol-Protein Interaction via Hydration-Enabled Enthalpy-Driven Binding Mechanism

    Science.gov (United States)

    Chong, Yuan; Kleinhammes, Alfred; Tang, Pei; Xu, Yan; Wu, Yue

    2015-01-01

    Water plays an important role in weak associations of small drug molecules with proteins. Intense focus has been on binding-induced structural changes in the water network surrounding protein binding sites, especially their contributions to binding thermodynamics. However, water is also tightly coupled to protein conformations and dynamics, and so far little is known about the influence of water-protein interactions on ligand binding. Alcohols are a type of low-affinity drugs, and it remains unclear how water affects alcohol-protein interactions. Here, we present alcohol adsorption isotherms under controlled protein hydration using in-situ NMR detection. As functions of hydration level, Gibbs free energy, enthalpy, and entropy of binding were determined from the temperature dependence of isotherms. Two types of alcohol binding were found. The dominant type is low-affinity nonspecific binding, which is strongly dependent on temperature and the level of hydration. At low hydration levels, this nonspecific binding only occurs above a threshold of alcohol vapor pressure. An increased hydration level reduces this threshold, with it finally disappearing at a hydration level of h~0.2 (g water/g protein), gradually shifting alcohol binding from an entropy-driven to an enthalpy-driven process. Water at charged and polar groups on the protein surface was found to be particularly important in enabling this binding. Although further increase in hydration has smaller effects on the changes of binding enthalpy and entropy, it results in significant negative change in Gibbs free energy due to unmatched enthalpy-entropy compensation. These results show the crucial role of water-protein interplay in alcohol binding. PMID:25856773

  15. Kinetic Evidence of an Apparent Negative Activation Enthalpy in an Organocatalytic Process

    Science.gov (United States)

    Han, Xiao; Lee, Richmond; Chen, Tao; Luo, Jie; Lu, Yixin; Huang, Kuo-Wei

    2013-08-01

    A combined kinetic and computational study on our tryptophan-based bifunctional thiourea catalyzed asymmetric Mannich reactions reveals an apparent negative activation enthalpy. The formation of the pre-transition state complex has been unambiguously confirmed and these observations provide an experimental support for the formation of multiple hydrogen bonding network between the substrates and the catalyst. Such interactions allow the creation of a binding cavity, a key factor to install high enantioselectivity.

  16. A Mixed Enthalpy-Temperature Finite Element Method For Generalized Phase-Change Problems

    DEFF Research Database (Denmark)

    krabbenhøft, Kristian; Damkilde, Lars

    2003-01-01

    In a large number of problems of engineering interest the transition of the material from one phase to another is of vital importance in describing the overall physical behaviour. Common applications include metal casting, freezing and thawing of foodstuffs and other biological materials, ground...... freezing and solar energy storage. The phase-change problem is characterized by an abrupt change in enthalpy per unit temperature in a narrow temperature range around the freezing point....

  17. Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Ruscic, Branko

    2015-07-16

    Active Thermochemical Tables (ATcT) thermochemistry for the sequential bond dissociations of methane, ethane, and methanol systems were obtained by analyzing and solving a very large thermochemical network (TN). Values for all possible C–H, C–C, C–O, and O–H bond dissociation enthalpies at 298.15 K (BDE298) and bond dissociation energies at 0 K (D0) are presented. The corresponding ATcT standard gas-phase enthalpies of formation of the resulting CHn, n = 4–0 species (methane, methyl, methylene, methylidyne, and carbon atom), C2Hn, n = 6–0 species (ethane, ethyl, ethylene, ethylidene, vinyl, ethylidyne, acetylene, vinylidene, ethynyl, and ethynylene), and COHn, n = 4–0 species (methanol, hydroxymethyl, methoxy, formaldehyde, hydroxymethylene, formyl, isoformyl, and carbon monoxide) are also presented. The ATcT thermochemistry of carbon dioxide, water, hydroxyl, and carbon, oxygen, and hydrogen atoms is also included, together with the sequential BDEs of CO2 and H2O. The provenances of the ATcT enthalpies of formation, which are quite distributed and involve a large number of relevant determinations, are analyzed by variance decomposition and discussed in terms of principal contributions. The underlying reasons for periodic appearances of remarkably low and/or unusually high BDEs, alternating along the dissociation sequences, are analyzed and quantitatively rationalized. The present ATcT results are the most accurate thermochemical values currently available for these species.

  18. Use of enthalpy and Gibbs free energy to evaluate the risk of amorphous formation.

    Science.gov (United States)

    Hsieh, Daniel S; Sarsfield, Beth A; Davidovich, Martha; DiMemmo, Lynn M; Chang, Shih-Ying; Kiang, San

    2010-09-01

    The control of crystalline and amorphous phases is important during the development of a new drug candidate. Our approach begins with an understanding of the thermodynamics of these two phases. We have developed a quantitative yet practical work flow consisting of three steps towards the analysis of the risk of amorphous material formation. First, we derive the thermodynamic equations to calculate the enthalpy, Gibbs free energy, and the solubility of each phase and their differences as a function of temperature. The enthalpy for each crystalline drug substance at its melting point is selected as the reference state to enable a consistent approach for all analysis. Second, we use data from DSC measurements and the derived thermodynamic equations to construct the enthalpy, Gibbs free energy and solubility diagrams so as to compare the characteristics of these two phases. Finally, we use the results of these calculations to evaluate the potential risk of crystalline-to-amorphous phase conversion during processing of either the drug substance or the drug product. In addition, the impact of amorphous formation on solubility is evaluated. Two drug candidates are used to illustrate this workflow for risk analysis.

  19. Spatial variability of enthalpy in broiler house during the heating phase

    Directory of Open Access Journals (Sweden)

    Patrícia F. P. Ferraz

    2016-06-01

    Full Text Available ABSTRACT The thermal environment inside a broiler house has a great influence on animal welfare and productivity during the production phase. Enthalpy is a thermodynamic property that has been proposed to evaluate the internal broiler house environment, for being an indicator of the amount of energy contained in a mixture of water vapor and dry air. Therefore, this study aimed to characterize the spatial variability of enthalpy in a broiler house during the heating phase using geostatistics. The experiment was conducted in the spring season, in a commercial broiler house with heating system consisting of two furnaces that heat the air indirectly, in the first 14 days of the birds' life. It was possible to characterize enthalpy variability using geostatistical techniques, which allowed observing the spatial dependence through kriging maps. The analyses of the maps allowed observing problems in the heating system in regions inside the broiler house, which may cause a thermal discomfort to the animals besides productive and economic losses.

  20. Enthalpies of proton adsorption onto Bacillus licheniformis at 25, 37, 50, and 75 °C

    Science.gov (United States)

    Gorman-Lewis, Drew

    2011-03-01

    Understanding bacterial surface reactivity requires many different lines of investigation. Toward this end, we used isothermal titration calorimetry to measure heats of proton adsorption onto a Gram positive thermophile Bacillus licheniformis at 25, 37, 50, and 75 °C. Proton adsorption under all conditions exhibited exothermic heat production. Below pH 4.5, exothermic heats decreased as temperature increased above 37 °C; above pH 4.5, there was no significant difference in heats evolved at the temperatures investigated. Total proton uptake did not vary significantly with temperature. Site-specific enthalpies and entropies were calculated by applying a 4-site, non-electrostatic surface complexation model to the calorimetric data. Interpretation of site-specific enthalpies and entropies of proton adsorption for site L1, L2, and L4 are consistent with previous interpretations of phosphoryl, carboxyl, and hydroxyl/amine site-identities, respectively, and with previous calorimetric measurements of proton adsorption onto mesophilic species. Enthalpies and entropies for surface site L3 are not consistent with the commonly inferred phosphoryl site-identity and are more consistent with sulfhydryl functional groups. These results reveal intricacies of surface reactivity that are not detectable by other methods.

  1. Effects of partitioned enthalpy of mixing on glass-forming ability.

    Science.gov (United States)

    Song, Wen-Xiong; Zhao, Shi-Jin

    2015-04-14

    We explore the inherent reason at atomic level for the glass-forming ability of alloys by molecular simulation, in which the effect of partitioned enthalpy of mixing is studied. Based on Morse potential, we divide the enthalpy of mixing into three parts: the chemical part (ΔEnn), strain part (ΔEstrain), and non-bond part (ΔEnnn). We find that a large negative ΔEnn value represents strong AB chemical bonding in AB alloy and is the driving force to form a local ordered structure, meanwhile the transformed local ordered structure needs to satisfy the condition (ΔEnn/2 + ΔEstrain) enthalpy of mixing is helpful to design a new metallic glass with a good glass forming ability. Moreover, two types of metallic glasses (i.e., "strain dominant" and "chemical dominant") are classified according to the relative importance between chemical effect and strain effect, which enriches our knowledge of the forming mechanism of metallic glass. Finally, a soft sphere model is established, different from the common hard sphere model.

  2. Cold-induced precipitation of a monoclonal IgM: a negative activation enthalpy reaction.

    Science.gov (United States)

    Meliga, Stefano C; Farrugia, William; Ramsland, Paul A; Falconer, Robert J

    2013-01-17

    Cold-induced precipitation of a monoclonal IgM cryoglobulin isolated from a patient with Waldenström's macroglobulinemia was observed to have a negative activation enthalpy. The rate of the reaction increased, as the temperature decreased. Differential scanning calorimetry of the monoclonal IgM showed precipitation as an inverted peak during a downward temperature scan. The transition temperature was between 14 and 15 °C and was possibly concentration dependent. At temperatures below the transition the precipitation was best described by second-order kinetics. The difference in change in enthalpy between precipitation and disassociation suggests that cold-induced precipitation had a fast precipitation stage followed by a slower consolidation reaction. Negligible curvature of the Eyring plot suggested the precipitation reaction was dominated by van der Waal forces and hydrogen bonding. Conversely, during an upward temperature scan, disassociation was observed as a positive enthalpy peak. This reaction had two stages, a reaction undoing consolidation followed by heat-induced disassociation that had first-order kinetics.

  3. Water networks contribute to enthalpy/entropy compensation in protein-ligand binding.

    Science.gov (United States)

    Breiten, Benjamin; Lockett, Matthew R; Sherman, Woody; Fujita, Shuji; Al-Sayah, Mohammad; Lange, Heiko; Bowers, Carleen M; Heroux, Annie; Krilov, Goran; Whitesides, George M

    2013-10-16

    The mechanism (or mechanisms) of enthalpy-entropy (H/S) compensation in protein-ligand binding remains controversial, and there are still no predictive models (theoretical or experimental) in which hypotheses of ligand binding can be readily tested. Here we describe a particularly well-defined system of protein and ligands--human carbonic anhydrase (HCA) and a series of benzothiazole sulfonamide ligands with different patterns of fluorination--that we use to define enthalpy/entropy (H/S) compensation in this system thermodynamically and structurally. The binding affinities of these ligands (with the exception of one ligand, in which the deviation is understood) to HCA are, despite differences in fluorination pattern, indistinguishable; they nonetheless reflect significant and compensating changes in enthalpy and entropy of binding. Analysis reveals that differences in the structure and thermodynamic properties of the waters surrounding the bound ligands are an important contributor to the observed H/S compensation. These results support the hypothesis that the molecules of water filling the active site of a protein, and surrounding the ligand, are as important as the contact interactions between the protein and the ligand for biomolecular recognition, and in determining the thermodynamics of binding.

  4. Constant Enthalpy Change Value during Pyrophosphate Hydrolysis within the Physiological Limits of NaCl*

    Science.gov (United States)

    Wakai, Satoshi; Kidokoro, Shun-ichi; Masaki, Kazuo; Nakasone, Kaoru; Sambongi, Yoshihiro

    2013-01-01

    A decrease in water activity was thought to result in smaller enthalpy change values during PPi hydrolysis, indicating the importance of solvation for the reaction. However, the physiological significance of this phenomenon is unknown. Here, we combined biochemistry and calorimetry to solve this problem using NaCl, a physiologically occurring water activity-reducing reagent. The pyrophosphatase activities of extremely halophilic Haloarcula japonica, which can grow at ∼4 m NaCl, and non-halophilic Escherichia coli and Saccharomyces cerevisiae were maximal at 2.0 and 0.1 m NaCl, respectively. Thus, halophilic and non-halophilic pyrophosphatases exhibit distinct maximal activities at different NaCl concentration ranges. Upon calorimetry, the same exothermic enthalpy change of −35 kJ/mol was obtained for the halophile and non-halophiles at 1.5–4.0 and 0.1–2.0 m NaCl, respectively. These results show that solvation changes caused by up to 4.0 m NaCl (water activity of ∼0.84) do not affect the enthalpy change in PPi hydrolysis. It has been postulated that PPi is an ATP analog, having a so-called high energy phosphate bond, and that the hydrolysis of both compounds is enthalpically driven. Therefore, our results indicate that the hydrolysis of high energy phosphate compounds, which are responsible for biological energy conversion, is enthalpically driven within the physiological limits of NaCl. PMID:23965994

  5. Extreme Entropy-Enthalpy Compensation in a Drug Resistant Variant of HIV-1 Protease

    Science.gov (United States)

    King, Nancy M.; Prabu-Jeyabalan, Moses; Bandaranayake, Rajintha M.; Nalam, Madhavi N. L.; Nalivaika, Ellen A.; Özen, Ayşegül; Haliloglu, Türkan; Yılmaz, Neşe Kurt; Schiffer, Celia A.

    2012-01-01

    The development of HIV-1 protease inhibitors has been the historic paradigm of rational structure-based drug design, where structural and thermodynamic analyses have assisted in the discovery of novel inhibitors. While the total enthalpy and entropy change upon binding determine the affinity, often the thermodynamics are considered in terms of inhibitor properties only. In the current study, profound changes are observed in the binding thermodynamics of a drug resistant variant compared to wild-type HIV-1 protease, irrespective of the inhibitor bound. This variant (Flap+) has a combination of flap and active site mutations and exhibits extremely large entropy-enthalpy compensation compared to wild-type protease, 5–15 kcal/mol, while losing only 1–3 kcal/mol in total binding free energy for any of six FDA approved inhibitors. Although entropy-enthalpy compensation has been previously observed for a variety of systems, never have changes of this magnitude been reported. The co-crystal structures of Flap+ protease with four of the inhibitors were determined and compared with complexes of both the wildtype protease and another drug resistant variant that does not exhibit this energetic compensation. Structural changes conserved across the Flap+ complexes, which are more pronounced for the flaps covering the active site, likely contribute to the thermodynamic compensation. The finding that drug resistant mutations can profoundly modulate the relative thermodynamic properties of a therapeutic target independent of the inhibitor presents a new challenge for rational drug design. PMID:22712830

  6. Constant enthalpy change value during pyrophosphate hydrolysis within the physiological limits of NaCl.

    Science.gov (United States)

    Wakai, Satoshi; Kidokoro, Shun-ichi; Masaki, Kazuo; Nakasone, Kaoru; Sambongi, Yoshihiro

    2013-10-11

    A decrease in water activity was thought to result in smaller enthalpy change values during PPi hydrolysis, indicating the importance of solvation for the reaction. However, the physiological significance of this phenomenon is unknown. Here, we combined biochemistry and calorimetry to solve this problem using NaCl, a physiologically occurring water activity-reducing reagent. The pyrophosphatase activities of extremely halophilic Haloarcula japonica, which can grow at ∼4 M NaCl, and non-halophilic Escherichia coli and Saccharomyces cerevisiae were maximal at 2.0 and 0.1 M NaCl, respectively. Thus, halophilic and non-halophilic pyrophosphatases exhibit distinct maximal activities at different NaCl concentration ranges. Upon calorimetry, the same exothermic enthalpy change of -35 kJ/mol was obtained for the halophile and non-halophiles at 1.5-4.0 and 0.1-2.0 M NaCl, respectively. These results show that solvation changes caused by up to 4.0 M NaCl (water activity of ∼0.84) do not affect the enthalpy change in PPi hydrolysis. It has been postulated that PPi is an ATP analog, having a so-called high energy phosphate bond, and that the hydrolysis of both compounds is enthalpically driven. Therefore, our results indicate that the hydrolysis of high energy phosphate compounds, which are responsible for biological energy conversion, is enthalpically driven within the physiological limits of NaCl.

  7. Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium-Nitrate Example.

    Science.gov (United States)

    Jin, Geng Bang; Lin, Jian; Estes, Shanna L; Skanthakumar, S; Soderholm, L

    2017-12-13

    The influence of countercations (A n+ ) in directing the composition of monomeric metal-ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of A n+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A + hydration enthalpies found for two related series of thorium (Th)-nitrate molecular compounds obtained by evaporating acidic aqueous Th-nitrate solutions in the presence of A + counterions. Analyses of their chemical composition and solid-state structures demonstrate that A + not only affects the overall solid-state packing of the Th-nitrato complexes but also influences the composition of the Th-nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A + hydration enthalpies, such that the A + with smaller hydration enthalpies associate with less hydrated and more anionic Th-nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of A n+ , opens a new avenue for the design and synthesis of targeted metal-ligand complexes.

  8. Solvation enthalpy and the thermodynamics of hydration of trans-cyclohexyl-1,4-diamine and cis-cyclohexyl-1,2-diamine

    Energy Technology Data Exchange (ETDEWEB)

    Tome, Luciana I.N.; Jesus, A.J. Lopes [Department of Chemistry, Rua Larga 3004-535, University of Coimbra (Portugal); Esteves de Castro, R.A. [Faculty of Pharmacy, Rua do Norte 3000-295, University of Coimbra (Portugal); Teixeira, M. Helena S.F. [Department of Chemistry, Rua Larga 3004-535, University of Coimbra (Portugal); Canotilho, Joao [Faculty of Pharmacy, Rua do Norte 3000-295, University of Coimbra (Portugal); Eusebio, M. Ermelinda S. [Department of Chemistry, Rua Larga 3004-535, University of Coimbra (Portugal)], E-mail: quierme@ci.uc.pt

    2007-10-15

    The enthalpy of solution of trans-cyclohexyl-1,4-diamine and cis-cyclohexyl-1,2-diamine in water was determined by calorimetry. The enthalpy of hydration was determined from this quantity and from the enthalpy of sublimation/vaporization presented in another paper by the authors. Considering the solvation process resulting from cavity creation in the solvent and variation of solute conformation transfer steps, the enthalpy corresponding to solute-solvent interaction was estimated. The entropies of solvation and interaction were calculated from the values given for the enthalpies in the present paper and those available for the Gibbs free energies.

  9. Low-enthalpy geothermal resources for electricity production: A demand-side management study for intelligent communities

    DEFF Research Database (Denmark)

    Xydis, George A.; Nanaki, Evanthia A.; Koroneos, Christopher J.

    2013-01-01

    The geological conditions in Greece contributed to the creation of important low-enthalpy geothermal energy resources (LEGERs). The resources are divided into low, medium and high enthalpy, or temperature, based on criteria that are generally based on the energy content of the fluid. LEGERs...... are those sources of the hot water whose temperature is between 25 and 100°C, which are used for heating residences and in the agricultural or industrial sector. The investigation for the exploitation of low-enthalpy geothermal fluids, which began around 1980, intensified in the last two decades. The low......-enthalpy geothermal potential in Greece is rather significant as most of the geothermal fields have been found in regions with favourable developmental conditions, and it seems that they do not present serious environmental or technical exploitation problems. LEGER areas are abundant in Greece, mainly in the eastern...

  10. Computations of Separated High-Enthalpy Hypersonic Flows: Development of RANS and Variable-Resolution PANS Approaches, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — We propose the development of a high fidelity computational approach for unsteady calculations of strongly separated non-equilibrium high-enthalpy hypersonic flows....

  11. Pressure and temperature dependence of excess enthalpies of methanol + tetraethylene glycol dimethyl ether and methanol + polyethylene glycol dimethyl ether 250

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, E.R.; Coxam, J.Y.; Fernandez, J.; Grolier, J.P.E.

    1999-12-01

    The excess molar enthalpies at 323.15 K, 373.15 K, and 423.15 K, at 8 MPa, are reported for the binary mixtures methanol + tetraethylene glycol dimethyl ether (TEGDME) and methanol + poly(ethylene glycol) dimethyl ether 250 (PEGDME 250). Excess molar enthalpies were determined with a Setaram C-80 calorimeter equipped with a flow mixing cell. For both systems, the excess enthalpies are positive over the whole composition range, increasing with temperature. The H{sup E}(x) curves are slightly asymmetrical, and their maxima are skewed toward the methanol-rich region. The excess enthalpies slightly change with the pressure, the sign of this change being composition-dependent. In the case of mixtures with TEGDME, the experimental H{sup E} values have been compared with those predicted with the Gmehling et al. version of UNIFAC (Dortmund) and the Nitta-Chao and DISQUAC group contribution models.

  12. LA PROYECCIÓN TALASOPOLÍTICA DE CHINA Y LAS DISPUTAS TERRITORIALES EN EL MAR MERIDIONAL

    Directory of Open Access Journals (Sweden)

    Lucas Pavez Rosales

    2017-04-01

    Full Text Available Este trabajo investigativo se funda en el objetivo de analizar la proyección talasopolítica de la República Popular China ( RPCh, en relación a las tensiones en el mar de la China meridional como yuxtaposición de intereses económicos y políticos entre los Estados involucrados. Siendo objetivos específicos: 1 dimensionar costos y factibilidad del creciente esfuerzo chino de configurarse como potencia marítima; 2 develar la unidad fragmentación de la postura de los miembros ASEAN frente a China, en la disputa; y 3 evidenciar la estrategia de EUA para hacer frente al cuestionamiento a su hegemonía en la región. A partir de esta base, el escrito busca dilucidar la forma en que el mar meridional se ha convertido en la nueva zona geopolítica caliente en el Sistema-mundo, y en la cual se puede producir una vorágine de conflictividad que desestabilice a la región.

  13. The Atlantic Meridional Transect: Spatially Extensive Calibration and Validation of Optical Properties and Remotely Sensed Measurements of Ocean Colour

    Science.gov (United States)

    Aiken, James; Hooker, Stanford

    1997-01-01

    Twice a year, the Royal Research Ship (RRS) James Clark Ross (JCR) steams a meridional transect of the atlantic Ocean between Grimsly (UK) and Stanley (Falkland Islands) with a port call in Montevideo (Uruguay), as part of the annual research activities of the British Antarctic Survey (BAS). In September, the JCR sails from the UK, and the following April it makes the return trip. The ship is operated by the BAS for the Natural Environment Research Council (NERC). The Atlantic Meridional Transect (AMT) Program exploits the passage of the JCR from approximately 50 deg. N to 50 deg. S with a primary objective to investigate physical and biological processes, as well as to measure the mesi-to-basin-scale bio-optical properties of the atlantic Ocean. The calibration and validation of remotely sensed observations of ocean colour is an inherent objective of these studies: first, by relating in situ measurements of water leaving radiance to satellite measurement, and second, by measuring the bio-optically active constituents of the water.

  14. Experimental and theoretical excess molar enthalpies of ternary and binary mixtures containing 2-Methoxy-2-Methylpropane, 1-propanol, heptane

    International Nuclear Information System (INIS)

    Mato, Marta M.; Cebreiro, Susana M.; Paz Andrade, María Inmaculada; Legido, José Luis

    2013-01-01

    Highlights: • Experimental enthalpies for the ternary system MTBE + propanol + heptane were measured. • No experimental ternary values were found in the currently available literature. • Experimental enthalpies for the binary system propanol + heptane were measured. • Excess molar enthalpies are positive over the whole range of composition. • The ternary contribution is also positive, and the representation is asymmetric. -- Abstract: Excess molar enthalpies, at the temperature of 298.15 K and atmospheric pressure, have been measured for the ternary system {x 1 2-Methoxy-2-Methylpropane (MTBE) + x 2 1-propanol + (1 − x 1 − x 2 ) heptane}, over the whole composition range. Also, experimental data of excess molar enthalpy for the involved binary mixture {x 1-propanol + (1 − x) heptane} at the 298.15 K and atmospheric pressure, are reported. We are not aware of any previous experimental measurement of excess enthalpy in the literature for the ternary system presented in this study. Values of the excess molar enthalpies were measured using a Calvet microcalorimeter. The ternary contribution to the excess enthalpy was correlated with the equation due to Morris et al. (1975) [15], and the equation proposed by Myers–Scott (1963) [14] was used to fitted the experimental binary mixture measured in this work. Additionally, the experimental results are compared with the estimations obtained by applying the group contribution model of UNIFAC, in the versions of Larsen et al. (1987) [16] and Gmehling et al. (1993) [17]. Several empirical expressions for estimating ternary properties from binary results were also tested

  15. ENTHALPY EU PROJECT: ENABLING THE DRYING PROCESS TO SAVE ENERGY AND WATER, REALISING PROCESS EFFICIENCY IN THE DAIRY CHAIN

    Directory of Open Access Journals (Sweden)

    Berta ALVAREZ PENEDO

    2016-11-01

    Full Text Available The EU funded ENTHALPY project aims to significantly reduce the consumption of water and energy in milk powder production to increase efficiency in the dairy production chain. Using a systematic approach, ENTHALPY project focusses on innovations within the post-harvest chain representing the highest energy and water consumption such as RF heating, solar thermal energy, mono-disperse atomising, dryer modelling, inline monitoring, enzymatic cleaning and membrane technology,

  16. An assessment of Antarctic Circumpolar Current and Southern Ocean meridional overturning circulation during 1958-2007 in a suite of interannual CORE-II simulations

    Science.gov (United States)

    Farneti, Riccardo; Downes, Stephanie M.; Griffies, Stephen M.; Marsland, Simon J.; Behrens, Erik; Bentsen, Mats; Bi, Daohua; Biastoch, Arne; Böning, Claus; Bozec, Alexandra; Canuto, Vittorio M.; Chassignet, Eric; Danabasoglu, Gokhan; Danilov, Sergey; Diansky, Nikolay; Drange, Helge; Fogli, Pier Giuseppe; Gusev, Anatoly; Hallberg, Robert W.; Howard, Armando; Ilicak, Mehmet; Jung, Thomas; Kelley, Maxwell; Large, William G.; Leboissetier, Anthony; Long, Matthew; Lu, Jianhua; Masina, Simona; Mishra, Akhilesh; Navarra, Antonio; George Nurser, A. J.; Patara, Lavinia; Samuels, Bonita L.; Sidorenko, Dmitry; Tsujino, Hiroyuki; Uotila, Petteri; Wang, Qiang; Yeager, Steve G.

    2015-09-01

    In the framework of the second phase of the Coordinated Ocean-ice Reference Experiments (CORE-II), we present an analysis of the representation of the Antarctic Circumpolar Current (ACC) and Southern Ocean meridional overturning circulation (MOC) in a suite of seventeen global ocean-sea ice models. We focus on the mean, variability and trends of both the ACC and MOC over the 1958-2007 period, and discuss their relationship with the surface forcing. We aim to quantify the degree of eddy saturation and eddy compensation in the models participating in CORE-II, and compare our results with available observations, previous fine-resolution numerical studies and theoretical constraints. Most models show weak ACC transport sensitivity to changes in forcing during the past five decades, and they can be considered to be in an eddy saturated regime. Larger contrasts arise when considering MOC trends, with a majority of models exhibiting significant strengthening of the MOC during the late 20th and early 21st century. Only a few models show a relatively small sensitivity to forcing changes, responding with an intensified eddy-induced circulation that provides some degree of eddy compensation, while still showing considerable decadal trends. Both ACC and MOC interannual variabilities are largely controlled by the Southern Annular Mode (SAM). Based on these results, models are clustered into two groups. Models with constant or two-dimensional (horizontal) specification of the eddy-induced advection coefficient κ show larger ocean interior decadal trends, larger ACC transport decadal trends and no eddy compensation in the MOC. Eddy-permitting models or models with a three-dimensional time varying κ show smaller changes in isopycnal slopes and associated ACC trends, and partial eddy compensation. As previously argued, a constant in time or space κ is responsible for a poor representation of mesoscale eddy effects and cannot properly simulate the sensitivity of the ACC and MOC

  17. Direct measurements of the enthalpy of solution of solid solute in supercritical fluids: study on the CO2-naphthalene system.

    Science.gov (United States)

    Zhang, X; Han, B; Zhang, J; Li, H; He, J; Yan, H

    2001-10-01

    A setup for a calorimeter for simultaneously measuring the solubility and the solution enthalpy of solid solutes in supercritical fluids (SCFs) has been established. The enthalpy of solution of naphthalene in supercritical CO2 was measured at 308.15 K in the pressure range from 8.0-11.0 MPa. It was found that the enthalpy of solution (deltaH) was negative in the pressure range from 8.0 to 9.5 MPa, and the absolute value decreased with increasing pressure. In this pressure range, the dissolution of the solute was enthalpy driven. However, the deltaH became positive at pressures higher than 9.5 MPa, and the dissolution was entropy driven. Monte Carlo simulation was performed to analyze the local structural environment of the solvated naphthalene molecules in supercritical CO2 under the experimental conditions for the calorimetric measurements. By combining the enthalpy data and the simulation results, it can be deduced that the energy level of CO2 in the high compressible region is higher than that at higher pressures, which results in the large negative enthalpy of solution and the larger degree of solvent-solute clustering in the high compressible region.

  18. Prediction of formation enthalpies for Al2X-type intermetallics using back-propagation neural network

    International Nuclear Information System (INIS)

    Sun, S.P.; Yi, D.Q.; Jiang, Y.; Wu, C.P.; Zang, B.; Li, Y.

    2011-01-01

    Research highlights: → An ANN was built to predict the formation enthalpies of Al 2 X-type intermetallics. → The values predicted by the ANN agree with experiments well to typically within 10%. → The method comparison suggests that our ANN method is superior to Miedema's model. → Some trends of formation enthalpies for Al 2 X-type intermetallics were observed. - Abstract: A back-propagation artificial neural network (ANN) was established to predict the formation enthalpies of Al 2 X-type intermetallics as a function of some physical parameters. These physical parameters include the electronegativity difference, the electron density difference, the atomic size difference, and the electron-atom ratio (e/a). The values calculated by the ANN method agree with experiments well to typically within 10%, indicating that the well-trained back-propagation (BP) neural network is feasible, and can precisely predict the formation enthalpies of Al 2 X-type intermetallics. The method comparison based on the predicted formation enthalpies suggests that our ANN method is superior to Miedema's model. Some trends of formation enthalpies for Al 2 X-type intermetallics were also observed from the ANN.

  19. Oceanic mass transport by mesoscale eddies.

    Science.gov (United States)

    Zhang, Zhengguang; Wang, Wei; Qiu, Bo

    2014-07-18

    Oceanic transports of heat, salt, fresh water, dissolved CO2, and other tracers regulate global climate change and the distribution of natural marine resources. The time-mean ocean circulation transports fluid as a conveyor belt, but fluid parcels can also be trapped and transported discretely by migrating mesoscale eddies. By combining available satellite altimetry and Argo profiling float data, we showed that the eddy-induced zonal mass transport can reach a total meridionally integrated value of up to 30 to 40 sverdrups (Sv) (1 Sv = 10(6) cubic meters per second), and it occurs mainly in subtropical regions, where the background flows are weak. This transport is comparable in magnitude to that of the large-scale wind- and thermohaline-driven circulation. Copyright © 2014, American Association for the Advancement of Science.

  20. Experimental measurement of enthalpy increments of Th0.25Ce0.75O2

    International Nuclear Information System (INIS)

    Babu, R.; Balakrishnan, S.; Ananthasivan, K.; Nagarajan, K.

    2013-01-01

    Thorium has been suggested as an alternative fertile material for a nuclear fuel cycle, and an inert matrix for burning plutonium and for waste disposal. The third stage of India's nuclear power programme envisages utilization of thorium and plutonium as a fuel in Advanced Heavy Water Reactor (AHWR) and Accelerator Driven Sub-critical Systems (ADSS). Solid solutions of ThO 2 -PuO 2 are of importance because of coexistence of Th with Pu during the breeding cycle. CeO 2 is used as a PuO 2 analog due to similar ionic radii of cations and similar physico-chemical properties of the oxides. ThO 2 forms a homogeneous solid solution with the cubic fluorite structure when doped with Ce in the entire compositional range. In the development of mixed oxide nuclear fuels, knowledge of thermodynamic properties of thorium oxide and its mixtures has become extremely importance for understanding the fuel behavior during irradiation and for predicting the performance of the fuel under accidental conditions. Thermodynamic functions such as the enthalpy increment and heat capacity of the theria-ceria solid solution have not been measured experimentally. Hence, the enthalpy increments of thoria-ceria solid solutions, Th 0.25 Ce 0.75 O 2 by inverse drop calorimetry in the temperature range 523-1723 K have been measured. The measured enthalpy increments were fitted in to polynomial functions by using the least squares method and the other thermodynamic functions such as heat capacity, entropy and Gibbs energy functions were computed in the temperature range 298-1800 K. The reported thermodynamic functions for Th 0.25 Ce 0.75 O 2 forms the first experimental data and the heat capacity of (Th,Ce)O 2 solid solutions was shown to obey the Neumann-Kopp's rule. (author)

  1. Enthalpy-driven nuclease-like activity and mechanism of peptide-chlorambucil conjugates.

    Science.gov (United States)

    Yang, Robin C K; Huang, Jonathan T B; Chen, Yu-Ling; Hung, Chia-Chun; Liao, Mokai; Yao, Wen-Chen; Chen, Chiu-Heng; Liou, Chien-Chung; Waring, Michael J; Sheh, Leung

    2014-07-21

    We report the results of attaching the anticancer drug chlorambucil (CLB) to two high-affinity DNA binding peptides: Met-Hyp-Arg-Lys-(Py)4-Lys-Arg-NH2 (HyM-10) and Gln-Hyp-Arg-Lys-(Py)4-Lys-Arg-NH2 (HyQ-10). These CLB-peptide conjugates cleave DNA very effectively and sequence-selectively without the use of chemicals, heat, or UV irradiation. Polyacrylamide gel electrophoresis identifies the sites where CLB-HyM-10 and CLB-HyQ-10 attack a complementary pair of 5'-(32)P-labeled duplexes derived from pBR322 in the absence of piperidine or other chemical additives. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) has confirmed the preferential cleavage sites as well as a novel stepwise cleavage mechanism of sequence-selective DNA cleavage. Resembling restriction endonucleases, the CLB-peptide conjugates appear to be capable of producing double strand DNA breaks. Circular dichroism studies show that CLB-HyM-10 and CLB-HyQ-10 induce significant local conformational changes in DNA via the minor groove, possibly with dimeric binding stoichiometry. The energetic basis of DNA binding by these conjugates has been investigated by isothermal titration calorimetry, revealing that the binding of both the peptides and their CLB conjugates is overwhelmingly enthalpy-driven. The maintenance of a conserved negative binding free energy in DNA-conjugate interactions is a crucial feature of the universal enthalpy-entropy compensation phenomenon. The strongly enthalpy-driven binding of CLB-peptide conjugates to preferred loci in DNA furnishes the required proximity effect to generate the observed nuclease-like sequence-selective cleavage.

  2. Seasonal Variability of Salt Transport During the Indian Ocean Monsoons

    Science.gov (United States)

    2011-08-27

    the global water budget which is one of the main forcing mechanisms of the thermohaline circulation . Increase in surface salinity when aided by deep...enced by water circulation and ocean-atmosphere coupled interactions such as the Maddcn-Julian Oscillation (MJO) [Joseph and Freeland, 2005]. As a...affects meridional circulation and aids the transport of salt [Sevellec et ai, 2008; Czaja, 2009]. Deep convection could be inhibited by the freshening

  3. Experimental study on an innovative enthalpy recovery technology based on indirect flash evaporative cooling

    DEFF Research Database (Denmark)

    Nie, Jinzhe; Yuan, Shu; Fang, Lei

    2018-01-01

    recovery unit. The principle of the technology is to over saturate indoor exhaust air by ultrasonic atomizing humidification. The evaporation of ultrafine mists cools down indoor exhaust air to its wet-bulb temperature and makes not only sensible heat transfer but also moisture condensed in outdoor supply...... were measured to investigate and analyze its energy recover efficiencies. The results showed that in hot and humid climate, up to 71% of total heat recover efficiency could be achieved by the prototype unit, and more than 50% of the enthalpy recovered was contributed by moisture condensation...

  4. Entropy–enthalpy compensation as a fundamental concept and analysis tool for systematical experimental data

    KAUST Repository

    Starikov, E.B.

    2012-06-01

    Enthalpy-entropy compensation (EEC) has a definite physical sense. Here, we review EEC from a new standpoint, using the notion of correlation. The latter has two basic meanings: (a) \\'A\\' is correlated to \\'B\\' means \\'A\\' results from \\'B\\' or vice versa; (b) this same means there is some real, but hidden \\'C\\' in connection to both \\'A\\' and \\'B\\'). In accordance with the interpretation (b), we try rationalizing EEC in terms of hidden, but physically real factors. © 2012 Elsevier B.V. All rights reserved.

  5. Overexpression, purification, and enthalpy of unfolding of ferricytochrome c552 from a psychrophilic microorganism.

    Science.gov (United States)

    Oswald, Victoria F; Chen, WeiTing; Harvilla, Paul B; Magyar, John S

    2014-02-01

    The psychrophilic, hydrocarbonoclastic microorganism Colwellia psychrerythraea is important in global nutrient cycling and bioremediation. In order to investigate how this organism can live so efficiently at low temperatures (~4°C), thermal denaturation studies of a small electron transfer protein from Colwellia were performed. Colwellia cytochrome c552 was overexpressed in Escherichia coli, isolated, purified, and characterized by UV-visible absorption spectroscopy. The melting temperature (Tm) and the van't Hoff enthalpy (ΔHvH) were determined. These values suggest an unexpectedly high stability for this psychrophilic cytochrome. Copyright © 2013 Elsevier Inc. All rights reserved.

  6. Free-flight measurement technique in the free-piston high-enthalpy shock tunnel.

    Science.gov (United States)

    Tanno, H; Komuro, T; Sato, K; Fujita, K; Laurence, S J

    2014-04-01

    A novel multi-component force-measurement technique has been developed and implemented at the impulse facility JAXA-HIEST, in which the test model is completely unrestrained during the test and thus experiences free-flight conditions for a period on the order of milliseconds. Advantages over conventional free-flight techniques include the complete absence of aerodynamic interference from a model support system and less variation in model position and attitude during the test itself. A miniature on-board data recorder, which was a key technology for this technique, was also developed in order to acquire and store the measured data. The technique was demonstrated in a HIEST wind-tunnel test campaign in which three-component aerodynamic force measurement was performed on a blunted cone of length 316 mm, total mass 19.75 kg, and moment of inertia 0.152 kgm(2). During the test campaign, axial force, normal forces, and pitching moment coefficients were obtained at angles of attack from 14° to 32° under two conditions: H0 = 4 MJ/kg, P0 = 14 MPa; and H0 = 16 MJ/kg, P0 = 16 MPa. For the first, low-enthalpy condition, the test flow was considered a perfect gas; measurements were thus directly compared with those obtained in a conventional blow-down wind tunnel (JAXA-HWT2) to evaluate the accuracy of the technique. The second test condition was a high-enthalpy condition in which 85% of the oxygen molecules were expected to be dissociated; high-temperature real-gas effects were therefore evaluated by comparison with results obtained in perfect-gas conditions. The precision of the present measurements was evaluated through an uncertainty analysis, which showed the aerodynamic coefficients in the HIEST low enthalpy test agreeing well with those of JAXA-HWT2. The pitching-moment coefficient, however, showed significant differences between low- and high-enthalpy tests. These differences are thought to result from high-temperature real-gas effects.

  7. Calcul des enthalpies d'interaction électrostatique de quelques ...

    African Journals Online (AJOL)

    Les enthalpies d'interaction électrostatique de cinq solutés polaires ont été calculées dans deux différents solvants apolaires : le cyclohexane et le tétrachlorure de carbone. Les molécules étudiées sont le paradioxane, le diéthyléther, le tétrahydrofurane, le cis-dichloroéthylène et le butanol. Les calculs ont été effectués, ...

  8. Excess enthalpy of monoethanolamine + ionic liquid mixtures: how good are COSMO-RS predictions?

    Science.gov (United States)

    Gonzalez-Miquel, Maria; Massel, Marjorie; DeSilva, Aruni; Palomar, Jose; Rodriguez, Francisco; Brennecke, Joan F

    2014-10-02

    Mixtures of ionic liquids (ILs) and molecular amines have been suggested for CO2 capture applications. The basic idea is to replace water, which volatilizes in the amine regeneration step and increases the parasitic energy load, with a nonvolatile ionic liquid solvent. To fully understand the thermodynamics of these systems, here experimental excess enthalpies for binary mixtures of monoethanolamine (MEA) and two ILs: 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [hmim][NTf2], and 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [OHemim][NTf2], were obtained by calorimetry, using a Setaram C80 calorimeter, over the whole range of compositions at 313.15 K. Since it is the temperature derivative of the Gibbs energy, enthalpy is a sensitive measure of intermolecular interactions. MEA + [hmim][NTf2] is endothermic and MEA + [OHemim][NTf2] is exothermic. The reliability of COSMO-RS to predict the excess enthalpy of the (MEA+IL) systems was tested based on the implementation of two different molecular models to define the structure of the IL: the IL as separate cation and anion [C+A] and the IL as a bonded single specie [CA]. Quantum-chemical calculations were performed to gain additional insight into the intermolecular interactions between the components of the mixture. For MEA + [hmim][NTf2] both the [C+A] and [CA] models predict endothermic behavior, but the [CA] model is in better agreement with the experimental results. For MEA + [OHemim][NTf2] the [C+A] model provides the best match to the experimental exothermic results. However, what is really surprising is that two different conformations of the cation-anion pair with nearly identical energies in the [CA] model result in completely different (exothermic vs endothermic) predictions of the excess enthalpy. Nonetheless, the results do show that the influence of the structure of the IL on the thermodynamic behavior of the mixture (endothermic vs exothermic) can be attributed

  9. Power-feedwater enthalpy operating domain for SBWR applying Monte Carlo simulation

    International Nuclear Information System (INIS)

    Quezada-Garcia, S.; Espinosa-Martinez, E.-G.; Vazquez-Rodriguez, A.; Varela-Ham, J.R.; Espinosa-Paredes, G.

    2014-01-01

    In this work the analyses of the feedwater enthalpy effects on reactor power in a simplified boiling water reactor (SBWR) applying a methodology based on Monte Carlo's simulation (MCS), is presented. The MCS methodology was applied systematically to establish operating domain, due that the SBWR are not yet in operation, the analysis of the nuclear and thermalhydraulic processes must rely on numerical modeling, with the purpose of developing or confirming the design basis and qualifying the existing or new computer codes to enable reliable analyses. (author)

  10. Binding the mammalian high mobility group protein AT-hook 2 to AT-rich deoxyoligonucleotides: enthalpy-entropy compensation.

    Science.gov (United States)

    Joynt, Suzanne; Morillo, Victor; Leng, Fenfei

    2009-05-20

    HMGA2 is a DNA minor-groove binding protein. We previously demonstrated that HMGA2 binds to AT-rich DNA with very high binding affinity where the binding of HMGA2 to poly(dA-dT)(2) is enthalpy-driven and to poly(dA)poly(dT) is entropy-driven. This is a typical example of enthalpy-entropy compensation. To further study enthalpy-entropy compensation of HMGA2, we used isothermal-titration-calorimetry to examine the interactions of HMGA2 with two AT-rich DNA hairpins: 5'-CCAAAAAAAAAAAAAAAGCCCCCGCTTTTTTTTTTTTTTTGG-3' (FL-AT-1) and 5'-CCATATATATATATATAGCCCCCGCTATATATATATATATGG-3' (FL-AT-2). Surprisingly, we observed an atypical isothermal-titration-calorimetry-binding curve at low-salt aqueous solutions whereby the apparent binding-enthalpy decreased dramatically as the titration approached the end. This unusual behavior can be attributed to the DNA-annealing coupled to the ligand DNA-binding and is eliminated by increasing the salt concentration to approximately 200 mM. At this condition, HMGA2 binding to FL-AT-1 is entropy-driven and to FL-AT-2 is enthalpy-driven. Interestingly, the DNA-binding free energies for HMGA2 binding to both hairpins are almost temperature independent; however, the enthalpy-entropy changes are dependent on temperature, which is another aspect of enthalpy-entropy compensation. The heat capacity change for HMGA2 binding to FL-AT-1 and FL-AT-2 are almost identical, indicating that the solvent displacement and charge-charge interaction in the coupled folding/binding processes for both binding reactions are similar.

  11. Mean zonal and meridional accelerations and mean heating induced by solar tides for equinox and solstice conditions

    International Nuclear Information System (INIS)

    Groves, G.V.; Forbes, J.M.

    1985-01-01

    Evaluations are presented of the momentum and energy flux divergences of the diurnal and semidiurnal tidal fields calculated by Forbes from 0 to 400 km altitude. Results are presented in the form of meridional cross-sections from 0 to 78 0 N or S latitude with a 6 0 latitude interval. Comparisons are made with evaluations of the momentum flux divergences of the diurnal tide by Miyahara and good agreement is obtained in the lower thermosphere (below about 130 km) but a large disparity arises in the upper thermosphere. In the lower thermosphere momentum flux divergences of the semidiurnal tide are comparable with those of the diurnal tide and should be included in general circulation calculations of the 90-120 km region. (author)

  12. L'«Atles lingüístic del valencià meridional i alacantí» (ALVA

    Directory of Open Access Journals (Sweden)

    Josep Tormo Colomina

    2015-07-01

    Full Text Available This paper is the official presentation, since the project was first started in 1978, of the forthcoming «Atles Lingüístic del Valencià Meridional i Alacantí» (ALVA (Linguistic Atlas of Southern Valencian and Alacantí, which so far had not been explicitly publicized. This paper, divided in two sections, includes the background of the author, the birth of the Atlas, the original questionnaire and its evolution, the network of towns studied, the aims of the project, the research method, the present questionnaire, the findings beyond the questionnaire, the cartographic representation and a brief set of maps and comments showing the importance that microatles with a very specific questionnaire may have in reduced contexts in certain peripheral areas.

  13. Dynamical relationship between wind speed magnitude and meridional temperature contrast: Application to an interannual oscillation in Venusian middle atmosphere GCM

    Science.gov (United States)

    Yamamoto, Masaru; Takahashi, Masaaki

    2018-03-01

    We derive simple dynamical relationships between wind speed magnitude and meridional temperature contrast. The relationship explains scatter plot distributions of time series of three variables (maximum zonal wind speed UMAX, meridional wind speed VMAX, and equator-pole temperature contrast dTMAX), which are obtained from a Venus general circulation model with equatorial Kelvin-wave forcing. Along with VMAX and dTMAX, UMAX likely increases with the phase velocity and amplitude of a forced wave. In the scatter diagram of UMAX versus dTMAX, points are plotted along a linear equation obtained from a thermal-wind relationship in the cloud layer. In the scatter diagram of VMAX versus UMAX, the apparent slope is somewhat steep in the high UMAX regime, compared with the low UMAX regime. The scatter plot distributions are qualitatively consistent with a quadratic equation obtained from a diagnostic equation of the stream function above the cloud top. The plotted points in the scatter diagrams form a linear cluster for weak wave forcing, whereas they form a small cluster for strong wave forcing. An interannual oscillation of the general circulation forming the linear cluster in the scatter diagram is apparent in the experiment of weak 5.5-day wave forcing. Although a pair of equatorial Kelvin and high-latitude Rossby waves with a same period (Kelvin-Rossby wave) produces equatorward heat and momentum fluxes in the region below 60 km, the equatorial wave does not contribute to the long-period oscillation. The interannual fluctuation of the high-latitude jet core leading to the time variation of UMAX is produced by growth and decay of a polar mixed Rossby-gravity wave with a 14-day period.

  14. O HORST DA MANTIQUEIRA MERIDIONAL: PROPOSTA DE COMPARTIMENTAÇÃO MORFOESTRUTURAL PARA SUA PORÇÃO MINEIRA

    Directory of Open Access Journals (Sweden)

    Roberto Marques Neto

    2017-08-01

    Full Text Available A Mantiqueira Meridional perfaz o sistema orográfico contínuo mais elevado de todo o Brasil Oriental. Sua gênese está ligada à reativação tectônica que acometeu a Plataforma Brasileira entre o Cretáceo e o Paleógeno orquestrada pela separação da paleoplaca Afro-brasileira e processos geodinâmicos associados, com posteriores reativações vinculadas à dinâmica neotectônica intraplaca e outros efeitos diastróficos oriundos de tectônica ressurgente e ativa. Dessa forma, a compartimentação morfoestrutural da Serra da Mantiqueira integra uma série de feições passivas a um vasto rol de evidências de controle morfotectônico sobrepostos às estruturas preexistentes. O presente artigo consiste numa proposta de compartimentação morfoestrutural para a porção da Mantiqueira Meridional contida no estado de Minas Gerais, enfatizando o controle morfoestrutural, o papel dos níveis de base regionais, e as estruturas tectônicas ativas afetando os diferentes compartimentos discernidos. A análise integrada entre os litotipos, os lineamentos estruturais, a rede de drenagem e os padrões de formas de relevo discerniu os seguintes compartimentos morfoestruturais: Patamares de Cimeira da Mantiqueira (desmembrados em sete subcompartimentos, Patamares Escalonados da Mantiqueira (dois subcompartimentos, Cristas Quartzíticas Festonadas e Rebordos Erosivos Dissecados.

  15. High enthalpy extraction experiments with Fuji-1 MHD blow-down facility

    Energy Technology Data Exchange (ETDEWEB)

    Okuno, Y.; Okamura, T.; Yoshikawa, K. [Tokyo Inst. of Technology, Yokohama (JP)] [and others

    1999-07-01

    Recent experimental results of closed cycle MHD electrical power generation with the Fuji-1 blow-down facility are presented. In the experiment with Disk-F4 MHD generator, which was conducted with a modified seed injection system in 1997, an enthalpy extraction ratio of 18.4% was successfully demonstrated with a large output power of 506 kW. This enthalpy extraction ratio is the highest among those achieved with the Fuji-1 facility. The experimental results also revealed the electrical characteristics of the generator installed in the blow-down facility. The decline in the output power and its recovery were observed at the early stage of the power generation run. This fact could be attributed to the attachment of seed material to the generator walls and to its detachment, related to the relatively slow rise in temperature on the wall surface. It was verified for the first time in the Fuji-1 experiment that the reduction of impurity contamination resulted in improvement in the generator performance. (Author)

  16. High precision calorimetry to determine the enthalpy of combustion of methane

    Energy Technology Data Exchange (ETDEWEB)

    Dale, Andrew; Lythall, Christopher; Aucott, John; Sayer, Courtnay [Office of Gas and Electricity Markets, Technical Directorate, 3 Tigers Road, South Wigston, LE18 4UX Leicester (United Kingdom)

    2002-01-31

    The enthalpy of combustion of methane is the most important property used in the determination of the calorific value of natural gas. Only two sets of values with high accuracy and precision and measured under appropriate conditions have been published since it was first determined in 1848. These studies were done by Rossini, at the National Bureau of Standards in the USA in 1931, and Pittam and Pilcher, at the University of Manchester in 1972. This report details the design and operation of a high precision constant-pressure gas burning calorimeter, based on the design of those used in the previous studies, to measure the superior enthalpy of combustion of ultra-high purity methane at 25C.The use of modern equipment and automatic data collection leads to a value, traceable to national standards, of 890.61kJmol{sup -1} with a combined standard uncertainty of 0.21kJmol{sup -1}. This is in full accord with the value of 890.63kJmol{sup -1} calculated from the average of Rossini's and Pittam and Pilcher's work (with a random uncertainty based on 1 S.D. of 0.53kJmol{sup -1})

  17. Measurements of Increased Enthalpies of Adsorption for Boron-Doped Activated Carbons

    Science.gov (United States)

    Gillespie, Andrew; Beckner, Matthew; Chada, Nagaraju; Schaeperkoetter, Joseph; Singh, Anupam; Lee, Mark; Wexler, Carlos; Burress, Jacob; Pfeifer, Peter

    2013-03-01

    Boron-doping of activated carbons has been shown to increase the enthalpies of adsorption for hydrogen as compared to their respective undoped precursors (>10kJ/mol compared to ca. 5kJ/mol). This has brought significant interest to boron-doped carbons for their potential to improve hydrogen storage. Boron-doped activated carbons have been produced using a process involving the deposition of decaborane (B10H14) and high-temperature annealing resulting in boron contents up to 15%. In this talk, we will present a systematic study of the effect that boron content has on the samples' structure, hydrogen sorption, and surface chemistry. Measurements have shown a significant increase in the areal hydrogen excess adsorption and binding energy. Experimental enthalpies of adsorption will be presented for comparison to theoretical predictions. Additionally, samples have been characterized by thermal gravimetric analysis, gas chromatography-mass spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. TGA and GC-MS results investigated the decomposition of the decaborane in the carbon. Boron-carbon bonds are shown in the FTIR and XPS spectra, indicating that boron has been incorporated into the carbon matrix. Work supported by DOE-EERE, Award No. DE-FG36-08GO18142

  18. Retrogradation enthalpy does not always reflect the retrogradation behavior of gelatinized starch.

    Science.gov (United States)

    Wang, Shujun; Li, Caili; Zhang, Xiu; Copeland, Les; Wang, Shuo

    2016-02-10

    Starch retrogradation is a term used to define the process in which gelatinized starch undergoes a disorder-to-order transition. A thorough understanding of starch retrogradation behavior plays an important role in maintaining the quality of starchy foods during storage. By means of DSC, we have demonstrated for the first time that at low water contents, the enthalpy change of retrograded starch is higher than that of native starch. In terms of FTIR and Raman spectroscopic results, we showed that the molecular order of reheated retrograded starch samples is lower than that of DSC gelatinized starch. These findings have led us to conclude that enthalpy change of retrograded starch at low water contents involves the melting of recrystallized starch during storage and residual starch crystallites after DSC gelatinization, and that the endothermic transition of retrograded starch gels at low water contents does not fully represent the retrogradation behavior of starch. Very low or high water contents do not favor the occurrence of starch retrogradation.

  19. Enthalpy-Entropy Compensation Effect in Chemical Kinetics and Experimental Errors: A Numerical Simulation Approach.

    Science.gov (United States)

    Perez-Benito, Joaquin F; Mulero-Raichs, Mar

    2016-10-06

    Many kinetic studies concerning homologous reaction series report the existence of an activation enthalpy-entropy linear correlation (compensation plot), its slope being the temperature at which all the members of the series have the same rate constant (isokinetic temperature). Unfortunately, it has been demonstrated by statistical methods that the experimental errors associated with the activation enthalpy and entropy are mutually interdependent. Therefore, the possibility that some of those correlations might be caused by accidental errors has been explored by numerical simulations. As a result of this study, a computer program has been developed to evaluate the probability that experimental errors might lead to a linear compensation plot parting from an initial randomly scattered set of activation parameters (p-test). Application of this program to kinetic data for 100 homologous reaction series extracted from bibliographic sources has allowed concluding that most of the reported compensation plots can hardly be explained by the accumulation of experimental errors, thus requiring the existence of a previously existing, physically meaningful correlation.

  20. Enthalpy of mixing of liquid systems for lead free soldering: Ni–Sb–Sn system

    Science.gov (United States)

    Elmahfoudi, A.; Fürtauer, S.; Sabbar, A.; Flandorfer, H.

    2012-01-01

    The partial and integral enthalpies of mixing of liquid ternary Ni–Sb–Sn alloys were determined along five sections xSb/xSn = 3:1, xSb/xSn = 1:1, xSb/xSn = 1:3, xNi/xSn = 1:4, and xNi/xSb = 1:4 at 1000 °C in a large compositional range using drop calorimetry techniques. The mixing enthalpy of Ni–Sb alloys was determined at the same temperature and described by a Redlich–Kister polynomial. The other binary data were carefully evaluated from literature values. Our measured ternary data were fitted on the basis of an extended Redlich–Kister–Muggianu model for substitutional solutions. Additionally, a comparison of these results to the extrapolation model of Toop is given. The entire ternary system shows exothermic values of ΔmixH ranging from approx. −1300 J/mol, the minimum in the Sb–Sn binary system down to approx. −24,500 J/mol towards Ni–Sb. No significant ternary interaction could be deduced from our data. PMID:23471085

  1. The Molecular Origin of Enthalpy/Entropy Compensation in Biomolecular Recognition.

    Science.gov (United States)

    Fox, Jerome M; Zhao, Mengxia; Fink, Michael J; Kang, Kyungtae; Whitesides, George M

    2018-03-05

    Biomolecular recognition can be stubborn; changes in the structures of associating molecules, or the environments in which they associate, often yield compensating changes in enthalpies and entropies of binding and no net change in affinities. This phenomenon-termed enthalpy/entropy (H/S) compensation-hinders efforts in biomolecular design, and its incidence-often a surprise to experimentalists-makes interactions between biomolecules difficult to predict. Although characterizing H/S compensation requires experimental care, it is unquestionably a real phenomenon that has, from an engineering perspective, useful physical origins. Studying H/S compensation can help illuminate the still-murky roles of water and dynamics in biomolecular recognition and self-assembly. This review summarizes known sources of H/S compensation (real and perceived) and lays out a conceptual framework for understanding and dissecting- and, perhaps, avoiding or exploiting-this phenomenon in biophysical systems. Expected final online publication date for the Annual Review of Biophysics Volume 47 is May 20, 2018. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

  2. Enthalpy-Entropy Compensation (EEC) Effect: Decisive Role of Free Energy.

    Science.gov (United States)

    Pan, Animesh; Kar, Tanmoy; Rakshit, Animesh K; Moulik, Satya P

    2016-10-03

    The "enthalpy-entropy compensation" (EEC) effect has been a long-standing fascinating yet unresolved phenomenon in chemical thermodynamics. The reasons for the observation of EEC are not clear. Various views such as empirical, extrathermodynamic, error-related, solvation, and so forth as reasons for the H/S linear correlation are floating. Statistical reasons and a hidden Carnot's cycle (involving microscopic "heating and cooling" machines) have also been proposed recently for the observation of EEC. In this work, we have attempted a different line of approach to understand and explain the phenomenon. In the EEC treatment, the enthalpy (ΔH) and entropy (ΔS) values of "similar processes" are considered keeping aside the role of the other important thermodynamic parameter, that is, the free energy (ΔG). Considering ΔG along with ΔH and ΔS, it is established that the conventional EEC plot is not appropriate and mathematically sound. Consideration of ΔG may account for correlations of different kinds, linear, nonlinear, and so forth. Reports of non- or anticompensation phenomenon also prevail in the literature. A realistic account of the role of ΔG along with ΔH and ΔS in the understanding of such EEC correlations using authentic literature data is presented and discussed herein. EEC has several facets. Planned studies on similar systems with a wide range of ΔG values are required for realistic evaluation of the EEC and antienthalpy entropy compensation manifestations.

  3. Absolute ion hydration enthalpies from absolute hardness and some VBT relationships

    Science.gov (United States)

    Kaya, Savaş; Fernandes de Farias, Robson

    2018-01-01

    In the present work, absolute hydration enthalpies are calculated from ion absolute hardness for a series of +1 and -1 ions. The calculated values are compared with those previously reported (Housecroft, 2017) [2] and relationships between Vm-1/3 and absolute hardness are stablished. The following empirical equations have been derived, for cations and anions, respectively: ΔhydHo = -(9.645 η+ + 245.930) and ΔhydHo = -(64.601 η- + 12.321). In such equations, η+ and η- are the absolute hardness. It is shown that for d block monocations (Cu+, Ag+ and Au+), hydration enthalpy is closely related with Clementi effective nuclear charge by the equation: ΔhydHo = -(9.645 η+ + 245.930) (Zeff/(n - 1)), where n is the main quantum number. Furthermore, is shown that a typical VBT parameter (Vm-1/3) is related with η+ and η- values and so, with the energies of the frontier orbitals, that is, is stablished a direct relationship between a structural parameter available by X-ray data and the energy of atomic/molecular orbitals.

  4. Thermodynamics of Aβ16-21 dissociation from a fibril: Enthalpy, entropy, and volumetric properties.

    Science.gov (United States)

    Rao Jampani, Srinivasa; Mahmoudinobar, Farbod; Su, Zhaoqian; Dias, Cristiano L

    2015-11-01

    Here, we provide insights into the thermodynamic properties of A β16-21 dissociation from an amyloid fibril using all-atom molecular dynamics simulations in explicit water. An umbrella sampling protocol is used to compute potentials of mean force (PMF) as a function of the distance ξ between centers-of-mass of the A β16-21 peptide and the preformed fibril at nine temperatures. Changes in the enthalpy and the entropic energy are determined from the temperature dependence of these PMF(s) and the average volume of the simulation box is computed as a function of ξ. We find that the PMF at 310 K is dominated by enthalpy while the entropic energy does not change significantly during dissociation. The volume of the system decreases during dissociation. Moreover, the magnitude of this volume change also decreases with increasing temperature. By defining dock and lock states using the solvent accessible surface area (SASA), we find that the behavior of the electrostatic energy is different in these two states. It increases (unfavorable) and decreases (favorable) during dissociation in lock and dock states, respectively, while the energy due to Lennard-Jones interactions increases continuously in these states. Our simulations also highlight the importance of hydrophobic interactions in accounting for the stability of A β16-21. © 2015 Wiley Periodicals, Inc.

  5. Investigation Flow Uniformity in a Supersonic Duct with High Enthalpy Flows

    Science.gov (United States)

    Balboni, John; Atler, Doug; Gokcen, Tahir; Hartman, G. Joseph (Technical Monitor)

    1995-01-01

    Flow uniformity in a high enthalpy facility is investigated. The scramjet research facility is composed of a rectangular combustor duct connected to a 100 MW electric arc air heater. The Mach 3.3 flow is accelerated through a two-dimensional contoured nozzle. Instream measurements were made with water-cooled Pitot probes and stagnation point heat flux gages at stream enthalpy levels ranging from 4 to 7 Mj/kg. Flow surveys were made on the flow centerline and off centerline in order to measure the three dimensional uniformity of the flow in the rectangular duct. Measurements indicated that although the flow in the aspect ratio 6:1 duct was relatively uniform on the centerline, three dimensional viscous effects were apparent near the corners. Flow through the nozzle and constant area duct was modeled computationally using a two dimensional, Navier-Stokes, reacting gas code. The computations predict that the flow in the test section is in vibrational equilibrium. The computed and measured Pitot pressure and heat flux profiles are in reasonable agreement with the experimental data.

  6. Outlet sampling measurement of mass flux, enthalpy and void fraction in rod bundles

    International Nuclear Information System (INIS)

    Sreepada, S.R.

    1979-01-01

    The thermal-hydraulic performance of nuclear reactor cores is based on semi-empirical correlations and the local thermal-hydraulic conditions of the coolant, inferred analytically (using computer codes such as COBRA) from the rod bundle averaged conditions. The experimental data on local conditions of the coolant, such as mass flux, enthalpy and void fraction are limited and do not cover a wide range of thermodynamic variables. The improvements in the experimental isokinetic sampling technique for the measurement of enthalpy and mass flux are presented. Experiments were carried out on a 16 rod bundle prototypical of a boiling water reactor. Measurements were carried out on two subchannels. The experimental data are presented. Measurements were compared with the predictions of the computer code COBRA. The areas of disagreement between the measurements and the code predictions are presented along with the suggested code improvements. A dissolved radio-active salt technique for the measurement of subchannel void fractions is developed. The details of the technique and experimental void fraction measurements are presented. Future improvements of the method are suggested

  7. Hydrate thermal dissociation behavior and dissociation enthalpies in methane-carbon dioxide swapping process

    DEFF Research Database (Denmark)

    Mu, Liang; von Solms, Nicolas

    2018-01-01

    The swapping of methane with carbon dioxide in hydrate has been proposed as a potential strategy for geologic sequestration of carbon dioxide and production of methane from natural hydrate deposits. However, this strategy requires a better understanding of the thermodynamic characteristics of CH4...... and CO2 hydrate as well as (CH4 + CO2) or (CH4 + CO2 + N2) mixed hydrates (since (CO2 + N2) gas mixture is often used as the swapping gas), along with the thermal physics property changes during gas exchange. In this study, a high pressure micro-differential scanning calorimetry (HP μ-DSC) was performed...... on synthesized gas hydrates to investigate the dissociation behavior of various hydrates. The hydrate dissociation enthalpies were determined by both μ-DSC measurement and Clapeyron equation. For the single guest molecule hydrate system, the average dissociation enthalpies of CH4 hydrate and CO2 hydrate measured...

  8. Vapor pressures and sublimation enthalpies of seven heteroatomic aromatic hydrocarbons measured using the Knudsen effusion technique

    Energy Technology Data Exchange (ETDEWEB)

    Goldfarb, Jillian L., E-mail: JillianLGoldfarb@gmail.co [Division of Engineering, Brown University, Providence, RI 02912 (United States); Suuberg, Eric M., E-mail: Eric_Suuberg@brown.ed [Division of Engineering, Brown University, Providence, RI 02912 (United States)

    2010-06-15

    The vapor pressures of seven heteroatom-containing cyclic aromatic hydrocarbons, ranging in molecular weight from (168.19 to 208.21) g . mol{sup -1} were measured over the temperature range of (301 to 486) K using the isothermal Knudsen effusion technique. The compounds measured include: anthraquinone, 9-fluorenone, 9-fluorenone oxime, phenoxazine, phenoxathiin, and 9H-pyrido[3,4-b]indole. These solid-state sublimation measurements provided values that are compared to vapor pressures of parent aromatic compounds (anthracene and fluorene) and to others with substituent groups in order to examine the effects of alcohol, ketone, pyridine, and pyrrole functionality on this property. The enthalpies and entropies of sublimation for each compound were determined from the Clausius-Clapeyron equation. Though there is no consistent trend in terms of the effects of substitutions on changes in the enthalpy or entropy of sublimation, we note that the prevalence of enthalpic or entropic driving forces on vapor pressure depend on molecule-specific factors and not merely molecular weight of the substituents.

  9. Determination of standard molar enthalpies of formation of SrMoO4 micro/nano structures

    International Nuclear Information System (INIS)

    Guo, Yunxiao; Fan, Gaochao; Huang, Zaiyin; Sun, Jilong; Wang, Lude; Wang, Tenghui; Chen, Jie

    2012-01-01

    Graphical abstract: Schematic illustration of thermochemical cycle between the nano and bulk reaction systems. Highlights: ► A thermochemical cycle was designed. ► Relationship of standard molar enthalpies of formation between micro/nano and bulk SrMoO 4 was gained. ► Microcalorimetry was used as a supplementary technology. ► Standard molar enthalpies of formation of the synthesized micro/nano SrMoO 4 were obtained. ► This novel approach can be used to other micro/nano materials. - Abstract: SrMoO 4 micro/nano structures were prepared by a simple reverse microemulsion method and were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscope (SEM). In order to associate standard molar enthalpies of formation of nano SrMoO 4 with bulk SrMoO 4 , the relationship of them was obtained through designing a thermochemical cycle according to thermodynamic potential function method. Combined with microcalorimetry, the standard molar enthalpies of formation of the synthesized micro/nano SrMoO 4 at 298.15 K were gained in this paper. And the variation of standard molar enthalpies of formation of micro/nano SrMoO 4 with different morphologies and sizes was discussed.

  10. Enthalpy of sublimation/vaporization of trans-cyclohexyl-1,4-diamine and cis-cyclohexyl-1,2-diamine

    Energy Technology Data Exchange (ETDEWEB)

    Tome, Luciana I.N.; Rosado, Mario T.S.; Nunes, Sandra C.C.; Maria, Teresa M.R. [Department of Chemistry, Rua Larga 3004-535, University of Coimbra (Portugal); Canotilho, Joao [Faculty of Pharmacy, Rua do Norte 3000-295, University of Coimbra (Portugal); Eusebio, M. Ermelinda S. [Department of Chemistry, Rua Larga 3004-535, University of Coimbra (Portugal)], E-mail: quierme@ci.uc.pt

    2007-10-15

    The molar enthalpy of sublimation, {delta}{sub cr}{sup g}H{sub m}{sup 0}, of trans-cyclohexyl-1,4-diamine and the molar enthalpy of vaporization, {delta}{sub l}{sup g}H{sub m}{sup 0}, of cis-cyclohexyl-1,2-diamine, at the temperature 298.15 K, were determined by calorimetry. {delta}{sub cr}{sup g}H{sub m}{sup 0}(T=298.15K)=(105.0{+-}0.8)kJ.mol{sup -1} was obtained for the trans-isomer and {delta}{sub l}{sup g}H{sub m}{sup 0}(T=298.15K)=(62.2{+-}1.0)kJ.mol{sup -1} for the cis form. The molar enthalpy of fusion of the first compound, at T = 342.1 K, was determined by differential scanning calorimetry. The molar enthalpy of vaporization of the 1,4-isomer was estimated by combining the value of the enthalpy of sublimation with that of the enthalpy of fusion. The values obtained for molar standard enthalpy of vaporization and those available for the enthalpy of the diamines in the gas state were used to calculate the difference between the enthalpies of both compounds in the liquid state.

  11. Enthalpies of solution of N,N,N',N'-tetramethylurea in amides, dimethylsulphoxide, and acetone at 298.15 K

    International Nuclear Information System (INIS)

    Ivanov, Evgeniy V.; Smirnov, Valeriy I.

    2008-01-01

    The enthalpies of solution Δ sol H m m were determined for N,N,N',N'-tetramethylurea in formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulphoxide, and acetone. Measurements were made at 298.15 K and molalities m = (0.004 to 0.031) mol . kg -1 with a precise isoperibol ampoule-type calorimeter. Standard enthalpies of solution Δ sol H m 0 and transfer Δ tr H m 0 from one solvent to another were computed. The enthalpies of solution of the solute in the hydrogen-non-bonding media were found to be endothermic and weak depending on the nature of methylation in a solvent molecule. It was concluded that the solvent proton-donor ability and existing steric hindrances for hydrogen bonding and other intermolecular interactions play the key role in solvation of tetramethylurea

  12. Atmospheric transport of pollution to the Arctic

    International Nuclear Information System (INIS)

    Iversen, T.

    1984-01-01

    If the atmospheric processes are assumed to be nearly adiabatic, the conclusion is that the possible source areas of Arctic air pollution detected at ground level have to be situated in areas with almost the same temperature as observed in the Arctic itself. Sources south of the polar front system can only contribute to high-altitude (or upper level) Arctic pollution. The amplitude and phase of long, planetary waves are important since they determine the position of the polar front, and provide conditions for meridional transport of air at certain longitudes

  13. Standard enthalpies of formation of selected Ru{sub 2}YZ Heusler compounds

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Ming, E-mail: myin1@hawk.iit.edu; Nash, Philip

    2015-06-15

    Highlights: • Standard enthalpies of formation of Ru{sub 2}YZ were measured using a drop calorimeter. • Result of L2{sub 1} structured compounds agrees with first principles data. • Lattice parameters and related phase relationships were consistent with literature data. • Ru{sub 2}HfSn, Ru{sub 2}TiSn, Ru{sub 2}VGa, Ru{sub 2}VSi, Ru{sub 2}VSn of L2{sub 1} structure were reported for the first time. - Abstract: The standard enthalpies of formation of selected ternary Ru-based Heusler compounds Ru{sub 2}YZ (Y = Fe, Hf, Mn, Ti, V; Z = Al, Ga, In, Si, Ge, Sn) were measured using high temperature direct reaction calorimetry. The measured enthalpies of formation (in kJ/mole of atoms) of the Heusler compounds are, Ru{sub 2}FeGe (−19.7 ± 3.3); Ru{sub 2}HfSn (−24.9 ± 3.6); Ru{sub 2}MnSi (−46.0 ± 2.6); Ru{sub 2}MnGe (−29.7 ± 1.0); Ru{sub 2}MnSn (−20.6 ± 2.4); Ru{sub 2}TiSi (−94.9 ± 4.0); Ru{sub 2}TiGe (−79.1 ± 3.2); Ru{sub 2}TiSn (−60.6 ± 1.8); Ru{sub 2}VSi (−55.9 ± 1.7);for the B2-structured compounds, Ru{sub 2}FeSi (−28.5 ± 0.8); Ru{sub 2}HfAl (−70.8 ± 1.9); Ru{sub 2}MnAl (−32.3 ± 1.9); Ru{sub 2}MnGa (−25.3 ± 3.0); Ru{sub 2}TiAl (−62.7 ± 3.5); Ru{sub 2}VAl (−30.9 ± 1.6); Ru{sub 2}ZrAl (−64.5 ± 1.5). Values were compared with those from published first principles calculations and the OQMD (Open Quantum Materials Database). Lattice parameters of these compounds were determined using X-ray diffraction analysis (XRD). Microstructures were identified using scanning electron microscopy (SEM) and Energy Dispersive Spectroscopy (EDS)

  14. Extremes temperatures and enthalpy in Finland and Sweden in a changing climate

    International Nuclear Information System (INIS)

    Venaelaeinen, A.; Saku, S.; Jylhae, K.; Nikulin, G.; Kjellstroem, E.; Baerring, L.

    2009-06-01

    Though risks caused by harsh weather conditions are taken into account in the planning of nuclear power plants, some exceptional weather events or combination of different events may prevent normal power operation and simultaneously endanger safe shutdown of the plant. Extreme weather events could influence, for example, the external power grid connection, emergency diesel generators (blockage of air intakes), ventilation and cooling of electric and electronics equipment rooms and the seawater intake. Due to the influence of an intensified greenhouse effect the climate is changing rapidly during the coming decades and this change is expected to have an influence also on the occurrence of extreme weather events. In this report we have examined extreme temperatures. Enthalpy is a parameter that combines air temperature and air humidity and it is used in the design of air conditioning systems. Therefore, we have included also return levels of enthalpy in our analysis. The influence of climate change on extreme temperatures is analysed based on regional climate model simulations. The reoccurrence times of high temperatures combined with high air humidity was analysed based on measurements made at five Finnish and three Swedish meteorological stations. Based on the observational records we find the 10 year return level of daily maximum temperature to be around 32 deg. C and the 100 year return level around 35 deg. C. If we look the return levels of warm and humid conditions then for example in Helsinki the 10 year return level of one week mean temperature in case mean air humidity is above 80% is 20.1 deg. C. The 10 year return level of daily maximum enthalpy is around 60 kJ/kg and the 100 year return level almost 70 kJ/kg. According to the climate model simulations the largest increase of 50-year return level of daily maximum temperature is found in southern Sweden and south-western Finland. By the end of this century the increase can be 3-5 deg. C. The largest change

  15. Extremes temperatures and enthalpy in Finland and Sweden in a changing climate

    Energy Technology Data Exchange (ETDEWEB)

    Venaelaeinen, A.; Saku, S.; Jylhae, K. (Finnish Meteorological Institute (Finland)); Nikulin, G.; Kjellstroem, E.; Baerring, L. (Swedish Meteorological Institute (Sweden))

    2009-06-15

    Though risks caused by harsh weather conditions are taken into account in the planning of nuclear power plants, some exceptional weather events or combination of different events may prevent normal power operation and simultaneously endanger safe shutdown of the plant. Extreme weather events could influence, for example, the external power grid connection, emergency diesel generators (blockage of air intakes), ventilation and cooling of electric and electronics equipment rooms and the seawater intake. Due to the influence of an intensified greenhouse effect the climate is changing rapidly during the coming decades and this change is expected to have an influence also on the occurrence of extreme weather events. In this report we have examined extreme temperatures. Enthalpy is a parameter that combines air temperature and air humidity and it is used in the design of air conditioning systems. Therefore, we have included also return levels of enthalpy in our analysis. The influence of climate change on extreme temperatures is analysed based on regional climate model simulations. The reoccurrence times of high temperatures combined with high air humidity was analysed based on measurements made at five Finnish and three Swedish meteorological stations. Based on the observational records we find the 10 year return level of daily maximum temperature to be around 32 deg. C and the 100 year return level around 35 deg. C. If we look the return levels of warm and humid conditions then for example in Helsinki the 10 year return level of one week mean temperature in case mean air humidity is above 80% is 20.1 deg. C. The 10 year return level of daily maximum enthalpy is around 60 kJ/kg and the 100 year return level almost 70 kJ/kg. According to the climate model simulations the largest increase of 50-year return level of daily maximum temperature is found in southern Sweden and south-western Finland. By the end of this century the increase can be 3-5 deg. C. The largest change

  16. Thermal dissociation behavior and dissociation enthalpies of methane-carbon dioxide mixed hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, T.H.; Kneafsey, T.J.; Rees, E.V.L.

    2011-02-15

    Replacement of methane with carbon dioxide in hydrate has been proposed as a strategy for geologic sequestration of carbon dioxide (CO{sub 2}) and/or production of methane (CH{sub 4}) from natural hydrate deposits. This replacement strategy requires a better understanding of the thermodynamic characteristics of binary mixtures of CH{sub 4} and CO{sub 2} hydrate (CH{sub 4}-CO{sub 2} mixed hydrates), as well as thermophysical property changes during gas exchange. This study explores the thermal dissociation behavior and dissociation enthalpies of CH{sub 4}-CO{sub 2} mixed hydrates. We prepared CH{sub 4}-CO{sub 2} mixed hydrate samples from two different, well-defined gas mixtures. During thermal dissociation of a CH{sub 4}-CO{sub 2} mixed hydrate sample, gas samples from the head space were periodically collected and analyzed using gas chromatography. The changes in CH{sub 4}-CO{sub 2} compositions in both the vapor phase and hydrate phase during dissociation were estimated based on the gas chromatography measurements. It was found that the CO{sub 2} concentration in the vapor phase became richer during dissociation because the initial hydrate composition contained relatively more CO{sub 2} than the vapor phase. The composition change in the vapor phase during hydrate dissociation affected the dissociation pressure and temperature; the richer CO{sub 2} in the vapor phase led to a lower dissociation pressure. Furthermore, the increase in CO{sub 2} concentration in the vapor phase enriched the hydrate in CO{sub 2}. The dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate was computed by fitting the Clausius-Clapeyron equation to the pressure-temperature (PT) trace of a dissociation test. It was observed that the dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate lays between the limiting values of pure CH{sub 4} hydrate and CO{sub 2} hydrate, increasing with the CO{sub 2} fraction in the hydrate phase.

  17. An Approach to the Estimation of Adsorption Enthalpies of Polycyclic Aromatic Hydrocarbons on Particle Surfaces.

    Science.gov (United States)

    Cochran, Richard E; Kubátová, Alena; Kozliak, Evguenii I

    2016-08-04

    Current atmospheric models incorporate the values of vaporization enthalpies, ΔHvap, obtained for neat standards, thus disregarding the matrix effects on volatilization. To test the adequacy of this approximation, this study measured enthalpies of vaporization for five polycyclic aromatic hydrocarbons (PAHs) in the form of neat standards (ΔHvap) as well as adsorbed on the surface of silica, graphite, and graphene particles (ΔHvap(eff)), by using simultaneous thermogravimetry-differential scanning calorimetry (TGA-DSC). Measurement of the corresponding activation energy values, Ea(vap) and Ea vap(eff), by TGA using a derivative method was shown to be the most reliable and practical way to assess ΔHvap and ΔHvap(eff). Enthalpies of adsorption (ΔHads) were then calculated from the differences between Ea(vap) and Ea vap(eff), thus paving a way to modeling the solid-gas phase partitioning in atmospheric particulate matter (PM). The PAH adsorption on silica particle surfaces (representing n-π* interactions) resulted in negative values of ΔHads, indicating significant interactions. For graphite particles, positive ΔHads values were obtained; i.e., PAHs did not interact with the particle surface as strongly as observed for PM. PAHs on the surface of graphene particles evaporated in two stages, with the bulk of the mass loss occurring at temperatures lower than those with the neat standard, just as on graphite. Yet, unlike graphite, a small PAH fraction did not evaporate until higher temperatures compared to case of the neat standards and other particle surfaces (37.4-145.7 K), signifying negative, more PM-relevant values of ΔHads, apparently reflecting π-π* interactions and ranging between -7.6 and +32.6 kJ mol(-1), i.e., even larger than for silica, -3.3 to +8.3 kJ mol(-1). Thus, current atmospheric models may underestimate the partitioning of organic species in the particle phase unless matrix adsorption is taken into account.

  18. Enthalpies of Dissolution of Crystalline Naproxen Sodium in Water and Potassium Hydroxide Aqueous Solutions at 298 K

    Science.gov (United States)

    Lytkin, A. I.; Chernikov, V. V.; Krutova, O. N.; Bychkova, S. A.; Volkov, A. V.; Skvortsov, I. A.

    2018-03-01

    The enthalpies of dissolution of crystalline naproxen sodium in water and aqueous solutions of KOH at 298.15 K are measured by direct calorimetric means in a wide range of concentrations. The acid-base properties of naproxen sodium at ionic strength I 0 and I = 0.1 (KNO3) and a temperature of 298.15 K are studied by spectrophotometric means. The concentration and thermodynamic dissociation constants are determined. The standard enthalpies of the formation of naproxen sodium and the products of its dissociation in aqueous solution are calculated.

  19. Interaction of Bile Salts with β-Cyclodextrins Reveals Nonclassical Hydrophobic Effect and Enthalpy-Entropy Compensation.

    Science.gov (United States)

    Paul, Bijan K; Ghosh, Narayani; Mukherjee, Saptarshi

    2016-04-28

    Herein, we present an endeavor toward exploring the lacuna underlying the host:guest chemistry of inclusion complex formation between bile salt(s) and β-cyclodextrin(s) (βCDs). An extensive thermodynamic investigation based on isothermal titration calorimetry (ITC) demonstrates a dominant contribution from exothermic enthalpy change (ΔH enthalpy-entropy compensation behavior showing indication for almost complete compensation. To this end, we have quantified the interaction of two bile salt molecules (namely, sodium deoxycholate and sodium glycocholate) with a series of varying chemical substituents on the host counterpart, namely, βCD, (2-hydroxypropyl)-βCD, and methyl βCD.

  20. Determination of molar enthalpy of sublimation in case of orotic acid as obtained from experimental and computational data

    Science.gov (United States)

    Marochkin, Ilya I.; Altova, Ekaterina P.; Chilingarov, Norbert S.; Vilkova, Anna L.; Shishkov, Igor F.

    2018-03-01

    Saturated vapor pressure, ln(p/Pa) = (-21316 ± 511)/(T/K)+(41.64 ± 0.11), and enthalpy of sublimation of orotic acid, Δsub Hm0 (Tm) = 177 ± 4 kJ/mol, were determined by means of Knudsen effusion mass spectrometry in the temperature range of 423÷493 K. The computational approaches supported the experimental results reported. The theoretical estimation of the gas-phase enthalpy of formation for orotic acid was done with different working reactions used.

  1. Influence of El Niño Wind Stress Anomalies on South Brazil Bight Ocean Volume Transports

    Directory of Open Access Journals (Sweden)

    Luiz Paulo de Freitas Assad

    2015-01-01

    Full Text Available The knowledge of wind stress variability could represent an important contribution to understand the variability over upper layer ocean volume transports. The South Brazilian Bight (SBB circulation had been studied by numerous researchers who predominantly attempted to estimate its meridional volume transport. The main objective and contribution of this study is to identify and quantify possible interannual variability in the ocean volume transport in the SBB induced by the sea surface wind stress field. A low resolution ocean global circulation model was implemented to investigate the volume transport variability. The results obtained indicate the occurrence of interannual variability in meridional ocean volume transports along three different zonal sections. These results also indicate the influence of a wind driven large-scale atmospheric process that alters locally the SBB and near-offshore region wind stress field and consequently causes interannual variability in the upper layer ocean volume transports. A strengthening of the southward flow in 25°S and 30°S was observed. The deep layer ocean volume transport in the three monitored sections indicates a potential dominance of other remote ocean processes. A small time lag between the integrated meridional volume transports changes in each monitored zonal section was observed.

  2. Set up an Arc Welding Code with Enthalpy Method in Upwind Scheme

    Science.gov (United States)

    Ho, Je-Ee.

    2010-05-01

    In this study, a numerical code with enthalpy method in upwind scheme is proposed to estimate the distribution of thermal stress in the molten pool, which is primarily determined by the type of the input power and travel speed of heating source. To predict the cracker deficit inside the workpiece, a simulated program satisfying the diagonal domination and Scarborough criterion provides a stable iteration. Meantime, an experimental performance, operated by robot arm "DR-400" to provide a steady and continuous arc welding, was also conducted to verify the simulated result. By surveying the consistence of molten pool bounded by contrast shade and simulated melting contour on the surface of workpiece, the validity of model proposed to predict the thermal cracker has been successfully identified.

  3. Stable isotope studies of some low enthalpy geothermal systems in Kenya

    Science.gov (United States)

    Tole, Mwakio P.

    Oxygen and hydrogen isotope compositions of some low enthalpy geothermal systems in Kenya have been determined. Plots on δ 18O versus δD diagrams show that the compositions do not deviate appreciably from local meteoric water values. This would indicate that local meteoric waters are heated at depth and rise to the surface without much interaction with the country rocks. This is interpreted to be the case for the geothermal systems at Majimoto and Narosura, which have salinities of less than 350 ppm TDS and calculated reservoir temperatures of less than 110°C. The geothermal systems at Kapedo and Homa mountain which have high salinities (> 2 000 ppm TDS) and relatively higher calculated reservoir temperatures (> 150° C) are interpreted to have been operating for long periods of time, such that the rocks through which the present day geothermal waters are circulating have attained isotopic equilibrium with local meteoric waters.

  4. Sub-Tg enthalpy relaxation in an unstable oxide glass former: insights into the structural heterogeneity

    DEFF Research Database (Denmark)

    Yue, Yuanzheng; Zhang, Yanfei

    Structural heterogeneity plays a crucial role in determining functionality of glasses. In this work we have found that the sub-Tg enthalpy relaxation pattern in a hyperquenched glass is highly sensitive to structural heterogeneity. As a consequence, the former can be used as an effective approach...... to detect and quantify the structural heterogeneity in glass-forming liquids. However, the chemical nature of structural heterogeneity should be revealed by other means such as high resolution microscopic and spectroscopic methods. To study the impact of the structural heterogeneity on the sub-Tg relaxation...... chemical features and degrees of structural heterogeneity in glass-forming liquids. This finding contributes to the microscopic origin of both the primary and secondary relaxation in terms of structural heterogeneity. Finally the results provide insights into the relation between structural heterogeneity...

  5. High enthalpy storage thermoset network with giant stress and energy output in rubbery state.

    Science.gov (United States)

    Fan, Jizhou; Li, Guoqiang

    2018-02-13

    Low output in stress and energy in rubbery state has been a bottleneck for wide-spread applications of thermoset shape memory polymers (SMPs). Traditionally, stress or energy storage in thermoset network is through entropy reduction by mechanical deformation or programming. We here report another mechanism for energy storage, which stores energy primarily through enthalpy increase by stretched bonds during programming. As compared to entropy-driven counterparts, which usually have a stable recovery stress from tenths to several MPa and energy output of several tenths MJ/m 3 , our rubbery network achieved a recovery stress of 17.0 MPa and energy output of 2.12 MJ/m 3 in bulk form. The giant stress and energy release in the rubbery state will enhance applications of thermoset SMPs in engineering structures and devices.

  6. Enhancing Entropy and Enthalpy Fluctuations to Drive Crystallization in Atomistic Simulations.

    Science.gov (United States)

    Piaggi, Pablo M; Valsson, Omar; Parrinello, Michele

    2017-07-07

    Crystallization is a process of great practical relevance in which rare but crucial fluctuations lead to the formation of a solid phase starting from the liquid. As in all first order first transitions, there is an interplay between enthalpy and entropy. Based on this idea, in order to drive crystallization in molecular simulations, we introduce two collective variables, one enthalpic and the other entropic. Defined in this way, these collective variables do not prejudge the structure into which the system is going to crystallize. We show the usefulness of this approach by studying the cases of sodium and aluminum that crystallize in the bcc and fcc crystalline structures, respectively. Using these two generic collective variables, we perform variationally enhanced sampling and well tempered metadynamics simulations and find that the systems transform spontaneously and reversibly between the liquid and the solid phases.

  7. Enthalpy By Energy Balance for Aerodynamic Heating Facility at NASA Ames Research Center Arc Jet Complex

    Science.gov (United States)

    Hightower, T. Mark; MacDonald, Christine L.; Martinez, Edward R.; Balboni, John A.; Anderson, Karl F.; Arnold, Jim O. (Technical Monitor)

    2002-01-01

    The NASA Ames Research Center (ARC) Arc Jet Facilities' Aerodynamic Heating Facility (AHF) has been instrumented for the Enthalpy By Energy Balance (EB2) method. Diagnostic EB2 data is routinely taken for all AHF runs. This paper provides an overview of the EB2 method implemented in the AHF. The chief advantage of the AHF implementation over earlier versions is the non-intrusiveness of the instruments used. For example, to measure the change in cooling water temperature, thin film 1000 ohm Resistance Temperature Detectors (RTDs) are used with an Anderson Current Loop (ACL) as the signal conditioner. The ACL with 1000 ohm RTDs allows for very sensitive measurement of the increase in temperature (Delta T) of the cooling water to the arc heater, which is a critical element of the EB2 method. Cooling water flow rates are measured with non-intrusive ultrasonic flow meters.

  8. Oxygen migration enthalpy likely limits oxide precipitate dissolution during tabula rasa

    Energy Technology Data Exchange (ETDEWEB)

    Looney, E. E.; Laine, H. S.; Youssef, A.; Jensen, M. A.; LaSalvia, V.; Stradins, P.; Buonassisi, T.

    2017-09-25

    In industrial silicon solar cells, oxygen-related defects lower device efficiencies by up to 20% (rel.). In order to mitigate these defects, a high-temperature homogenization anneal called tabula rasa (TR) that has been used in the electronics industry is now proposed for use in solar-grade wafers. This work addresses the kinetics of tabula rasa by elucidating the activation energy governing oxide precipitate dissolution, which is found to be 2.6 +/- 0.5 eV. This value is consistent within uncertainty to the migration enthalpy of oxygen interstitials in silicon, implying TR to be kinetically limited by oxygen point-defect diffusion. This large activation energy is observed to limit oxygen precipitate dissolution during standard TR conditions, suggesting that more aggressive annealing conditions than conventionally used are required for complete bulk microdefect mitigation.

  9. Surface Catalysis and Oxidation on Stagnation Point Heat Flux Measurements in High Enthalpy Arc Jets

    Science.gov (United States)

    Nawaz, Anuscheh; Driver, David M.; Terrazas-Salinas

    2013-01-01

    Heat flux sensors are routinely used in arc jet facilities to determine heat transfer rates from plasma plume. The goal of this study is to assess the impact of surface composition changes on these heat flux sensors. Surface compositions can change due to oxidation and material deposition from the arc jet. Systematic surface analyses of the sensors were conducted before and after exposure to plasma. Currently copper is commonly used as surface material. Other surface materials were studied including nickel, constantan gold, platinum and silicon dioxide. The surfaces were exposed to plasma between 0.3 seconds and 3 seconds. Surface changes due to oxidation as well as copper deposition from the arc jets were observed. Results from changes in measured heat flux as a function of surface catalycity is given, along with a first assessment of enthalpy for these measurements. The use of cupric oxide is recommended for future heat flux measurements, due to its consistent surface composition arc jets.

  10. Thermogravimetric determination of the enthalpy of astatine and radon adsorption on palladium surfaces

    International Nuclear Information System (INIS)

    Eichler, B.; Son Chun, K.

    1985-01-01

    In order to investigate the adsorption of astatine and radon on a palladium surface some on- and off-line thermochromatographic experiments were carried out with 210 At and 220 Rn tracers. The partial molar adsorption enthalpy for zero covering was found to be ΔH/sub a//sup 0, loc./(At) = -(15S +- 10) kJ mole -1 and ΔH/sub a//sup 0, mob./(Rn) = -(37 +- 4) kJ mole -1 . The results are compared with theoretical and experimental values for other elements of the sixth period. The adsorption behaviour of At is in conformity with that of the p-metals on a palladium surface. (author)

  11. A moderate enthalpy and a low pollution load in healthy buildings

    DEFF Research Database (Denmark)

    Fanger, Povl Ole

    1998-01-01

    complaints caused by individual differences. The building should be acknowledged as a source of pollution and this source should be minimized during design by the selection of proper building materials and HVAC components. To improve ventilation effctiveness, supply of air close to the breathing zone of each......For the design of healthy buildings with a comfortable indoor environment, some general recommendations are provided. New research highlights the importance of controlling the enthalpy of indoor air at a moderate level, i.e., by controlling air temperature and relative humidity at a rather low...... level, still compatible with thermal comfort. A decrement of air temperature or humidity improves the perceived air quality and may decrease the required ventilation rate. A moderate air temperature and humidity plus individual control by radiation and conduction is recommended in order to decrease...

  12. Standard formation enthalpies of mononuclear and cluster oxoanions of boron, silicon and phosphorus

    International Nuclear Information System (INIS)

    Glybin, V.P.; Svirko, L.K.

    2000-01-01

    Standard formation enthalpies of boron, silicon and phosphorus are calculated. For calculations thermochemical method in conjunction with potential energy model of oxoanions in approximation of valence-force field of molecules and crystals are used. In the model of valence-force field ion-covalent crystals are considered as population of clusters of molecular type the number of which is equal to number of translation-nonequivalent atoms in the lattice dipped in nonhomogeneous electrostatic field of long-range interactions. For gaseous oxoanions field created by end oxygen atoms or other ones on which negative charge of anions is localized serves as equivalent of nonhomogeneous electrostatic field. In such approach potential energy of oxoanion is equal to sum of energy of electrostatic repulsion of negatively charged atoms and energy of valent element-oxygen bonds in neutral cluster [ru

  13. Enhancing Entropy and Enthalpy Fluctuations to Drive Crystallization in Atomistic Simulations

    Science.gov (United States)

    Piaggi, Pablo M.; Valsson, Omar; Parrinello, Michele

    2017-07-01

    Crystallization is a process of great practical relevance in which rare but crucial fluctuations lead to the formation of a solid phase starting from the liquid. As in all first order first transitions, there is an interplay between enthalpy and entropy. Based on this idea, in order to drive crystallization in molecular simulations, we introduce two collective variables, one enthalpic and the other entropic. Defined in this way, these collective variables do not prejudge the structure into which the system is going to crystallize. We show the usefulness of this approach by studying the cases of sodium and aluminum that crystallize in the bcc and fcc crystalline structures, respectively. Using these two generic collective variables, we perform variationally enhanced sampling and well tempered metadynamics simulations and find that the systems transform spontaneously and reversibly between the liquid and the solid phases.

  14. Determination of the vacancy formation enthalpy in chromium by positron annihilation

    International Nuclear Information System (INIS)

    Loper, G.D.; Smedskjaer, L.C.; Chason, M.K.; Siegel, R.W.

    1985-01-01

    Doppler broadening of the positron annihilation lineshape in 99.99 at. % pure chromium was measured over the temperature range 296 to 2049 0 K. The chromium sample was encapsulated in sapphire owing to its high vapor pressure near melting. Saturation-like behavior of the lineshape was observed near the melting temperature (2130 0 K). A two-state trapping model fit to the data yielded a vacancy formation enthalpy of 2.0 +- 0.2 eV. This result is discussed in relation to extant empirical relations for vacancy migration and self-diffusion in metals and to data from previous self-diffusion and annealing experiments in chromium. It is concluded that the observed vacancy ensemble is unlikely to be responsible for the measured self-diffusion behavior. The implications of the present results in terms of our understanding of mechanisms for self-diffusion in chromium and other refractory bcc metals are discussed

  15. Enthalpy-entropy compensation for n-hexane adsorption on Y zeolite containing transition metal cations

    Directory of Open Access Journals (Sweden)

    Hercigonja R.

    2015-01-01

    Full Text Available In this work, the values of entropy changes related to n-hexane adsorption onto cation exchanged Y zeolite were calculated from differential heats. Various transition metal cations (Co2+, Ni2+, Zn2+ and Cd2+ were introduced into the lattice of the parent NaY, and the existence of enthalpy-entropy compensation effect related to n-hexane adsorption, id. est, the linearity of -ΔH vs. -ΔS plots was examined. The compensation effect was confirmed for all investigated zeolites. The compensation effect can be comprehended as governed by ion-induced dipole interaction between highly polarizing cationic centers in zeolite and nonopolar n-hexane molecules. Finally, the compensation effect and so the compensation temperature were found to depend on the type of charge-balancing cation (charge, size and electronic configuration. [Projekat Ministarstva nauke Republike Srbije, br. 172018

  16. Reduced enthalpy of metal hydride formation for Mg-Ti nanocomposites produced by spark discharge generation.

    Science.gov (United States)

    Anastasopol, Anca; Pfeiffer, Tobias V; Middelkoop, Joost; Lafont, Ugo; Canales-Perez, Roger J; Schmidt-Ott, Andreas; Mulder, Fokko M; Eijt, Stephan W H

    2013-05-29

    Spark discharge generation was used to synthesize Mg-Ti nanocomposites consisting primarily of a metastable body-centered-cubic (bcc) alloy of Mg and Ti. The bcc Mg-Ti alloy transformed upon hydrogenation into the face-centered-cubic fluorite Mg1-yTiyHx phase with favorable hydrogen storage properties. Both metal and metal hydride nanocomposites showed a fractal-like porous morphology, with a primary particle size of 10-20 nm. The metal content of 70 atom % (at %) Mg and 30 at % Ti, consistently determined by XRD, TEM-EDS, and ICP-OES, was distributed uniformly across the as-prepared sample. Pressure-composition isotherms for the Mg-Ti-H nanocomposites revealed large differences in the thermodynamics relative to bulk MgH2, with a much less negative enthalpy of formation of the hydride as small as -45 ± 3 kJ/molH2 as deduced from van't Hoff plots. The plateau pressures of hydrogenation were substantially higher than those for bulk MgH2 in the low temperature range from 150 to 250 °C. The reaction entropy was simultaneously reduced to values down to 84 ± 5 J/K mol H2, following a linear relationship between the enthalpy and entropy. Plausible mechanisms for the modified thermodynamics are discussed, including the effect of lattice strains, the presence of interfaces and hydrogen vacancies, and the formation of excess free volume due to local deformations. These mechanisms all rely on the finely interdispersed nanocomposite character of the samples which is maintained by grain refinement.

  17. An evaluation for harnessing low-enthalpy geothermal energy in the Limpopo Province, South Africa

    Directory of Open Access Journals (Sweden)

    Taufeeq Dhansay

    2014-03-01

    Full Text Available South Africa generates most of its energy requirements from coal, and is now the leading carbon emitter in Africa, and has one of the highest rates of emissions of all nations in the world. In an attempt to decrease its CO2 emissions, South Africa continues to research and develop alternative forms of energy, expand on the development of nuclear and has began to explore potentially vast shale gas reserves. In this mix, geothermal has not been considered to date as an alternative energy source. This omission appears to stem largely from the popular belief that South Africa is tectonically too stable. In this study, we investigated low-enthalpy geothermal energy from one of a number of anomalously elevated heat flow regions in South Africa. Here, we consider a 75-MW enhanced geothermal systems plant in the Limpopo Province, sustainable over a 30-year period. All parameters were inculcated within a levelised cost of electricity model that calculates the single unit cost of electricity and tests its viability and potential impact toward South Africa's future energy security and CO2 reduction. The cost of electricity produced is estimated at 14 USc/KWh, almost double that of coal-generated energy. However, a USD25/MWh renewable energy tax incentive has the potential of making enhanced geothermal systems comparable with other renewable energy sources. It also has the potential of CO2 mitigation by up to 1.5 gCO2/KWh. Considering the aggressive nature of the global climate change combat and South Africa's need for a larger renewable energy base, low-enthalpy geothermal energy could potentially form another energy option in South Africa's alternative energy basket.

  18. The glass transition and enthalpy recovery of a single polystyrene ultrathin film using Flash DSC.

    Science.gov (United States)

    Koh, Yung P; Simon, Sindee L

    2017-05-28

    The kinetics of the glass transition are measured for a single polystyrene ultrathin film of 20 nm thickness using Flash differential scanning calorimetry (DSC). T g is measured over a range of cooling rates from 0.1 to 1000 K/s and is depressed compared to the bulk. The depression decreases with increasing cooling rate, from 12 K lower than the bulk at 0.1 K/s to no significant change at 1000 K/s. Isothermal enthalpy recovery measurements are performed from 50 to 115 °C, and from these experiments, the temperature dependence of the induction time along the glass line is obtained, as well as the temperature dependence of the time scale required to reach equilibrium, providing a measure of the shortest effective glassy relaxation time and the longest effective equilibrium relaxation time, respectively. The induction time for the ultrathin film is found to be similar to the bulk at all temperatures presumably because the T g values are the same due to the use of a cooling rate of 1000 K/s prior to the enthalpy recovery measurements. On the other hand, the times required to reach equilibrium for the ultrathin film and bulk are similar at 100 °C, and considerably shorter for the ultrathin film at 90 °C, consistent with faster dynamics under nanoconfinement at low temperatures. The magnitude of the "T g depression" is smaller when using the equilibrium relaxation time from the structural recovery experiment as a measure of the dynamics than when measuring T g after a cooling experiment. A relaxation map is developed to summarize the results.

  19. Measuring Enthalpy of Sublimation of Volatiles by Means of Piezoelectric Crystal Microbalances.

    Science.gov (United States)

    Dirri, Fabrizio; Palomba, Ernesto; Longobardo, Andrea; Zampetti, Emiliano

    2017-12-01

    Piezoelectric Crystal Microbalances (PCM's) are widely used to study the chemical processes involving volatile compounds in any environment, such as condensation process. Since PCM's are miniaturized sensor, they are very suitable for planetary in situ missions, where can be used to detect and to measure the mass amount of astrobiologically significant compounds, such as water and organics. This work focuses on the realization and testing of a new experimental setup, able to characterize volatiles which can be found in a planetary environment. In particular the enthalpy of sublimation of some dicarboxylic acids has been measured. The importance of dicarboxylic acids in planetology and astrobiology is due to the fact that they have been detected in carbonaceous chondritic material (e.g. Murchinson), among the most pristine material present in our Solar System. In this work, a sample of acid was heated in an effusion cell up to its sublimation. For a set of temperatures (from 30 °C to 75 °C), the deposition rate on the PCM surface has been measured. From these measurements, it has been possible to infer the enthalpy of sublimation of Adipic acid, i.e. ΔH = 141.6 ± 0.8 kJ/mol and Succinic acid, i.e. ΔH = 113.3 ± 1.3 kJ/mol. This technique has so demonstrated to be a good choice to recognise a single compound or a mixture (with an analysis upstream) even if some improvements concerning the thermal stabilization of the system will be implemented in order to enhance the results' accuracy. The experiment has been performed in support of the VISTA (Volatile In Situ Thermogravimetry Analyzer) project, which is included in the scientific payload of the ESA MarcoPolo-R mission study.

  20. Exploiting a water network to achieve enthalpy-driven, bromodomain-selective BET inhibitors.

    Science.gov (United States)

    Shadrick, William R; Slavish, Peter J; Chai, Sergio C; Waddell, Brett; Connelly, Michele; Low, Jonathan A; Tallant, Cynthia; Young, Brandon M; Bharatham, Nagakumar; Knapp, Stefan; Boyd, Vincent A; Morfouace, Marie; Roussel, Martine F; Chen, Taosheng; Lee, Richard E; Kiplin Guy, R; Shelat, Anang A; Potter, Philip M

    2018-01-01

    Within the last decade, the Bromodomain and Extra-Terminal domain family (BET) of proteins have emerged as promising drug targets in diverse clinical indications including oncology, auto-immune disease, heart failure, and male contraception. The BET family consists of four isoforms (BRD2, BRD3, BRD4, and BRDT/BRDT6) which are distinguished by the presence of two tandem bromodomains (BD1 and BD2) that independently recognize acetylated-lysine (KAc) residues and appear to have distinct biological roles. BET BD1 and BD2 bromodomains differ at five positions near the substrate binding pocket: the variation in the ZA channel induces different water networks nearby. We designed a set of congeneric 2- and 3-heteroaryl substituted tetrahydroquinolines (THQ) to differentially engage bound waters in the ZA channel with the goal of achieving bromodomain selectivity. SJ830599 (9) showed modest, but consistent, selectivity for BRD2-BD2. Using isothermal titration calorimetry, we showed that the binding of all THQ analogs in our study to either of the two bromodomains was enthalpy driven. Remarkably, the binding of 9 to BRD2-BD2 was marked by negative entropy and was entirely driven by enthalpy, consistent with significant restriction of conformational flexibility and/or engagement with bound waters. Co-crystallography studies confirmed that 9 did indeed stabilize a water-mediated hydrogen bond network. Finally, we report that 9 retained cytotoxicity against several pediatric cancer cell lines with EC 50 values comparable to BET inhibitor (BETi) clinical candidates. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains.

    Science.gov (United States)

    Jeong, Cheol; Douglas, Jack F

    2015-10-14

    The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ∼ M(β), is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from -1.8 to -2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature Tg where dynamic heterogeneity does not complicate the description of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔHa and entropy ΔSa of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a "critical" chain length, n ≈ 17. A close examination of this phenomenon indicates that a "buckling transition" from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔSa ∝ ΔHa, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔHa and ΔSa with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement.

  2. The glass transition and enthalpy recovery of a single polystyrene ultrathin film using Flash DSC

    Science.gov (United States)

    Koh, Yung P.; Simon, Sindee L.

    2017-05-01

    The kinetics of the glass transition are measured for a single polystyrene ultrathin film of 20 nm thickness using Flash differential scanning calorimetry (DSC). Tg is measured over a range of cooling rates from 0.1 to 1000 K/s and is depressed compared to the bulk. The depression decreases with increasing cooling rate, from 12 K lower than the bulk at 0.1 K/s to no significant change at 1000 K/s. Isothermal enthalpy recovery measurements are performed from 50 to 115 °C, and from these experiments, the temperature dependence of the induction time along the glass line is obtained, as well as the temperature dependence of the time scale required to reach equilibrium, providing a measure of the shortest effective glassy relaxation time and the longest effective equilibrium relaxation time, respectively. The induction time for the ultrathin film is found to be similar to the bulk at all temperatures presumably because the Tg values are the same due to the use of a cooling rate of 1000 K/s prior to the enthalpy recovery measurements. On the other hand, the times required to reach equilibrium for the ultrathin film and bulk are similar at 100 °C, and considerably shorter for the ultrathin film at 90 °C, consistent with faster dynamics under nanoconfinement at low temperatures. The magnitude of the "Tg depression" is smaller when using the equilibrium relaxation time from the structural recovery experiment as a measure of the dynamics than when measuring Tg after a cooling experiment. A relaxation map is developed to summarize the results.

  3. Enthalpy-Driven RNA Folding: Single-Molecule Thermodynamics of Tetraloop–Receptor Tertiary Interaction†

    Science.gov (United States)

    Fiore, Julie L.; Kraemer, Benedikt; Koberling, Felix; Edmann, Rainer; Nesbitt, David J.

    2010-01-01

    RNA folding thermodynamics are crucial for structure prediction, which requires characterization of both enthalpic and entropic contributions of tertiary motifs to conformational stability. We explore the temperature dependence of RNA folding due to the ubiquitous GAAA tetraloop–receptor docking interaction, exploiting immobilized and freely diffusing single-molecule fluorescence resonance energy transfer (smFRET) methods. The equilibrium constant for intramolecular docking is obtained as a function of temperature (T = 21–47 °C), from which a van’t Hoff analysis yields the enthalpy (ΔH°) and entropy (ΔS°) of docking. Tetraloop–receptor docking is significantly exothermic and entropically unfavorable in 1 mM MgCl2 and 100 mM NaCl, with excellent agreement between immobilized (ΔH° = −17.4 ± 1.6 kcal/mol, and ΔS° = −56.2 ± 5.4 cal mol−1 K−1) and freely diffusing (ΔH° = −17.2 ± 1.6 kcal/mol, and ΔS° = −55.9 ± 5.2 cal mol−1 K−1) species. Kinetic heterogeneity in the tetraloop–receptor construct is unaffected over the temperature range investigated, indicating a large energy barrier for interconversion between the actively docking and nondocking subpopulations. Formation of the tetraloop–receptor interaction can account for ~60% of the ΔH° and ΔS° of P4–P6 domain folding in the Tetrahymena ribozyme, suggesting that it may act as a thermodynamic clamp for the domain. Comparison of the isolated tetraloop–receptor and other tertiary folding thermodynamics supports a theme that enthalpy- versus entropy-driven folding is determined by the number of hydrogen bonding and base stacking interactions. PMID:19186984

  4. Evaluation of the ground surface Enthalpy balance from bedrock temperatures (Livingston Island, Maritime Antarctic

    Directory of Open Access Journals (Sweden)

    M. Ramos

    2009-05-01

    Full Text Available The annual evolution of the ground temperatures from Incinerador borehole in Livingston Island (South Shetlands, Antarctic is studied. The borehole is 2.4 m deep and is located in a massive quartzite outcrop with negligible water content, in the proximity of the Spanish Antarctic Station Juan Carlos I. In order to model the movement of the 0°C isotherm (velocity and maximum depth hourly temperature profiles from: (i the cooling periods of the frost season of 2000 to 2005, and (ii the warming periods of the thaw season of 2002–2003, 2003–2004 and 2004–2005, were studied. In this modelling approach, heat gains and losses across the ground surface are assumed to be the causes for the 0°C isotherm movement. A methodological approach to calculate the ground Enthalpy change based on the thermodynamic analysis of the ground during the cooling and warming periods is proposed. The Enthalpy change into the rock is equivalent to the heat exchange through the ground surface during each season, thus enabling to describe the interaction ground-atmosphere and providing valuable data for studies on permafrost and periglacial processes. The bedrock density and thermal conductivity are considered to be constant and initial isothermal conditions at 0°C are assumed (based in collected data and local meteorological conditions in this area to run the model in the beginning of each season. The final stages correspond to the temperatures at the end of the cooling and warming periods (annual minima and maxima. The application of this method avoids error propagation induced by the heat exchange calculations from multiple sensors using the Fourier method.

  5. Piezoelectric crystal microbalance measurements of enthalpy of sublimation of C2-C9 dicarboxylic acids

    Science.gov (United States)

    Dirri, F.; Palomba, E.; Longobardo, A.; Zampetti, E.

    2016-02-01

    We present here a novel experimental set-up that is able to measure the enthalpy of sublimation of a given compound by means of piezoelectric crystal microbalances (PCMs). The PCM sensors have already been used for space measurements, such as for the detection of organic and non-organic volatile species and refractory materials in planetary environments. In Earth atmospherics applications, PCMs can be also used to obtain some physical-chemical processes concerning the volatile organic compounds (VOCs) present in atmospheric environments. The experimental set-up has been developed and tested on dicarboxylic acids. In this work, a temperature-controlled effusion cell was used to sublimate VOC, creating a molecular flux that was collimated onto a cold PCM. The VOC recondensed onto the PCM quartz crystal, allowing the determination of the deposition rate. From the measurements of deposition rates, it has been possible to infer the enthalpy of sublimation of adipic acid, i.e. ΔHsub : 141.6 ± 0.8 kJ mol-1, succinic acid, i.e. 113.3 ± 1.3 kJ mol-1, oxalic acid, i.e. 62.5 ± 3.1 kJ mol-1, and azelaic acid, i.e. 124.2 ± 1.2 kJ mol-1. The results obtained show an accuracy of 1 % for succinic, adipic, and azelaic acid and within 5 % for oxalic acid and are in very good agreement with previous works (within 6 % for adipic, succinic, and oxalic acid and within 11 % or larger for azelaic acid).

  6. Effect of temperature on the dilution enthalpies of α,ω-amino acids in aqueous solutions

    International Nuclear Information System (INIS)

    Romero, C.M.; Cadena, J.C.; Lamprecht, I.

    2011-01-01

    Highlights: → The dilution of 3-amino propanoic acid, 4-amino butanoic acid, 5-amino pentanoic acid, and 6-amino hexanoic acid in water is an exothermic process at T = (293.15, 298.15, 303.15, and 308.15) K. → The limiting experimental slopes of the enthalpies of dilution with respect to the molality change Δm, are negative suggesting that the solutes interact with water primarily through their alkyl groups. → The value of the pairwise coefficient is positive at the temperatures considered, and the magnitude increases linearly with the number of methylene groups. → The comparison between the pairwise interaction coefficients for α,ω-amino acids and α-amino acids shows that the change in the enthalpic interaction coefficient is related to the relative position of the polar groups. - Abstract: Dilution enthalpies of aqueous solutions of 3-amino propanoic acid, 4-amino butanoic acid, 5-amino pentanoic acid, and 6-amino hexanoic acid were determined at T = (293.15, 298.15, 303.15, and 308.15) K using an LKB flow microcalorimeter. The homotactic interaction coefficients were obtained according to the McMillan-Mayer theory from the experimental data. For all the systems studied, the dilution of α,ω-amino acids in water is an exothermic process; the pair coefficients have positive values which increases with chain length. The obtained values of the interaction coefficients are interpreted in terms of solute-solvent and solute-solute interactions and are used as indicative of hydrophobic behavior of the amino acid studied.

  7. Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains

    Science.gov (United States)

    Jeong, Cheol; Douglas, Jack F.

    2015-10-01

    The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ˜ Mβ, is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from -1.8 to -2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature Tg where dynamic heterogeneity does not complicate the description of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔHa and entropy ΔSa of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a "critical" chain length, n ≈ 17. A close examination of this phenomenon indicates that a "buckling transition" from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔSa ∝ ΔHa, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔHa and ΔSa with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement.

  8. Non-kinematic Flux-transport Dynamos Including the Effects of Diffusivity Quenching

    Energy Technology Data Exchange (ETDEWEB)

    Ichimura, Chiaki; Yokoyama, Takaaki [Department of Earth and Planetary Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan)

    2017-04-10

    Turbulent magnetic diffusivity is quenched when strong magnetic fields suppress turbulent motion in a phenomenon known as diffusivity quenching. Diffusivity quenching can provide a mechanism for amplifying magnetic field and influencing global velocity fields through Lorentz force feedback. To investigate this effect, we conducted mean field flux-transport dynamo simulations that included the effects of diffusivity quenching in a non-kinematic regime. We found that toroidal magnetic field strength is amplified by up to approximately 1.5 times in the convection zone as a result of diffusivity quenching. This amplification is much weaker than that in kinematic cases as a result of Lorentz force feedback on the system’s differential rotation. While amplified toroidal fields lead to the suppression of equatorward meridional flow locally near the base of the convection zone, large-scale equatorward transport of magnetic flux via meridional flow, which is the essential process of the flux-transport dynamo, is sustainable in our calculations.

  9. Surface mapping, organic matter and water stocks in peatlands of the Serra do Espinhaço meridional - Brazil

    Directory of Open Access Journals (Sweden)

    Márcio Luiz da Silva

    2013-10-01

    Full Text Available Peatlands are soil environments that store carbon and large amounts of water, due to their composition (90 % water, low hydraulic conductivity and a sponge-like behavior. It is estimated that peat bogs cover approximately 4.2 % of the Earth's surface and stock 28.4 % of the soil carbon of the planet. Approximately 612 000 ha of peatlands have been mapped in Brazil, but the peat bogs in the Serra do Espinhaço Meridional (SdEM were not included. The objective of this study was to map the peat bogs of the northern part of the SdEM and estimate the organic matter pools and water volume they stock. The peat bogs were pre-identified and mapped by GIS and remote sensing techniques, using ArcGIS 9.3, ENVI 4.5 and GPS Track Maker Pro software and the maps validated in the field. Six peat bogs were mapped in detail (1:20,000 and 1:5,000 by transects spaced 100 m and each transect were determined every 20 m, the UTM (Universal Transverse Mercator coordinates, depth and samples collected for characterization and determination of organic matter, according to the Brazilian System of Soil Classification. In the northern part of SdEM, 14,287.55 ha of peatlands were mapped, distributed over 1,180,109 ha, representing 1.2 % of the total area. These peatlands have an average volume of 170,021,845.00 m³ and stock 6,120,167 t (428.36 t ha-1 of organic matter and 142,138,262 m³ (9,948 m³ ha-1 of water. In the peat bogs of the Serra do Espinhaço Meridional, advanced stages of decomposing (sapric organic matter predominate, followed by the intermediate stage (hemic. The vertical growth rate of the peatlands ranged between 0.04 and 0.43 mm year-1, while the carbon accumulation rate varied between 6.59 and 37.66 g m-2 year-1. The peat bogs of the SdEM contain the headwaters of important water bodies in the basins of the Jequitinhonha and San Francisco Rivers and store large amounts of organic carbon and water, which is the reason why the protection and preservation

  10. Liquid-Liquid Equilibrium and Excess Enthalpies in the Binary System 2-Methylpentane + N,N-Dimethylformamide

    Czech Academy of Sciences Publication Activity Database

    Bendová, Magdalena; Řehák, K.; Matouš, J.; Novák, J. P.

    2004-01-01

    Roč. 49, č. 5 (2004), s. 1318-1322 ISSN 0021-9568 Institutional research plan: CEZ:AV0Z4072921 Keywords : liquid-liquid equilibrium * excess enthalpies * thermodynamic models Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.368, year: 2004

  11. Liquid-Liquid Equilibrium and Excess Enthalpies in Binary Systems Methylcyclohexane plus Methanol and Methylcyclohexane plus N,N-Dimethylformamide

    Czech Academy of Sciences Publication Activity Database

    Bendová, Magdalena; Řehák, K.; Matouš, J.; Novák, J. P.

    2003-01-01

    Roč. 48, č. 1 (2003), s. 152-157 ISSN 0021-9568 Institutional research plan: CEZ:AV0Z4072921 Keywords : liquid-liquid equilibrium * excess enthalpy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.950, year: 2003

  12. Activation enthalpy of self-diffusion in pure metals interpreted as a measure of their interatomic force constant

    International Nuclear Information System (INIS)

    Turkdogan, E.T.

    2002-01-01

    The present study of self-diffusion data for pure solid elements has revealed that the diffusivities of body centered cubic (b.c.c.), face centered cubic (f.c.c.) and hexagonal close packed (h.c.p.) metals at their melting point temperatures (T m ) do relate in a systematic manner to the atomic number of the elements and their Period numbers. Also, the activation enthalpy of self-diffusion varies in a regular manner with the atomic number and Period number of the elements. It is surmised from these regularities that the activation enthalpy (Q) of self-diffusion may be considered as a direct measure of the interatomic force constant ε/k = (φ/R)T m where φ = Q/T m is the enthalpy coefficient. For solid metals ε/k = (15 to 19) T m , K; for non-metals the T m coefficient is (20 to 35), for rare-earth metals (10 to 13) and for liquid metals (3.32 ± 0.24). A comparison is made of these ε/k values with those derived from the standard enthalpies of dissociation of inorganic compounds to the constituent elements. A critical assessment is made of the experimental self-diffusion data for pure elements which conform to the observed regularities in the self-diffusion parameters in relation to the atomic number and Period number of the elements. (author)

  13. Enthalpy measurement using calorimetry shows a significant difference in potential energy between the active and latent conformations of PAI-1.

    Science.gov (United States)

    Sherman, Westley A; Blouse, Grant E; Perron, Michel J; Tran, Timothy; Shore, Joseph D; Gafni, Ari

    2005-02-01

    A central feature of the serpin inhibition mechanism is insertion of the reactive center loop into the central beta-sheet (beta-sheet A). This insertion also occurs when the reactive center loop is cleaved without protease inhibition. Using this effect, we have measured the enthalpy (DeltaH) of loop cleavage and insertion for plasminogen activator inhibitor 1 (PAI-1) as -38 kcal/mol. Because loop insertion can be blocked by incorporating a peptide into the central beta-sheet, it was possible to assign -7 kcal/mol to loop cleavage and -31 kcal/mol to loop insertion. These values are lower than values reported for the serpins alpha 1 -proteinase inhibitor and antithrombin of -53 to -63 kcal/mol, respectively, for loop insertion with negligible enthalpy for loop cleavage. A free energy difference of -9 kcal/mol has been reported between the active and spontaneously loop inserted "latent forms" of PAI-1, which is significantly smaller in magnitude than the -31 kcal/mol of enthalpy we measured for loop insertion. Because the enthalpy should relate closely to those regions of PAI-1 that have moved to lower potential energy, a difference distance matrix is presented that identifies regions of PAI-1 that move during loop insertion.

  14. Determination of saturation pressure and enthalpy of vaporization of semi-volatile aerosols: the integrated volume mentod

    Science.gov (United States)

    This study presents the integrated volume method for estimating saturation pressure and enthalpy of vaporization of a whole aerosol distribution. We measure the change of total volume of an aerosol distribution between a reference state and several heated states, with the heating...

  15. Computational investigation of enthalpy-entropy compensation in complexation of glycoconjugated bile salts with β-cyclodextrin and analogs.

    Science.gov (United States)

    Tidemand, Kasper D; Schönbeck, Christian; Holm, René; Westh, Peter; Peters, Günther H

    2014-09-18

    The inclusion complexes of glycoconjugated bile salts with β-cyclodextrin (β-CD) and 2-hydroxypropyl-β-cyclodextrins (HP-β-CD) in aqueous solution were investigated by molecular dynamics simulations to provide a molecular explanation of the experimentally observed destabilizing effect of the HP substituents. Good agreement with experimental data was found with respect to penetration depths of CDs. An increased degree of HP substitution (DS) resulted in an increased probability of blocking the cavity opening, thereby hindering the bile salt from entering CD. Further, the residence time of water molecules in the cavity increased with the DS. Release of water from the cavity resulted in a positive enthalpy change, which correlates qualitatively with the experimentally determined increase in complexation enthalpy and contributes to the enthalpy-entropy compensation. The positive change in complexation entropy with DS was not able to compensate for this unfavorable change in enthalpy induced by the HP substituents, resulting in a destabilizing effect. This was found to originate from fixation of the HP substituents and decreased free rotation of the bile salts within the CD cavities.

  16. Controlling the enthalpy-entropy competition in supramolecular fullerene liquid crystals by tuning the flexible chain length.

    Science.gov (United States)

    Zhu, Tiantian; Zhang, Xiaoyan; Li, Zhikai; Hsu, Chih-Hao; Chen, Wei; Miyoshi, Toshikazu; Li, Xiaohong; Yang, Xiaoming; Tu, Yingfeng; Li, Christopher Y

    2017-07-20

    We present here that in two-dimensional (2D) fullerene supramolecular liquid crystals (SLCs), the phase diagram and lamella thickness of SLCs and 2D crystals can be tuned by the flexible alkyl tail and spacer length, due to their different effects on enthalpy and entropy changes during SLC formation.

  17. Computation of binding energies including their enthalpy and entropy components for protein-ligand complexes using support vector machines.

    Science.gov (United States)

    Koppisetty, Chaitanya A K; Frank, Martin; Kemp, Graham J L; Nyholm, Per-Georg

    2013-10-28

    Computing binding energies of protein-ligand complexes including their enthalpy and entropy terms by means of computational methods is an appealing approach for selecting initial hits and for further optimization in early stages of drug discovery. Despite the importance, computational predictions of thermodynamic components have evaded attention and reasonable solutions. In this study, support vector machines are used for developing scoring functions to compute binding energies and their enthalpy and entropy components of protein-ligand complexes. The binding energies computed from our newly derived scoring functions have better Pearson's correlation coefficients with experimental data than previously reported scoring functions in benchmarks for protein-ligand complexes from the PDBBind database. The protein-ligand complexes with binding energies dominated by enthalpy or entropy term could be qualitatively classified by the newly derived scoring functions with high accuracy. Furthermore, it is found that the inclusion of comprehensive descriptors based on ligand properties in the scoring functions improved the accuracy of classification as well as the prediction of binding energies including their thermodynamic components. The prediction of binding energies including the enthalpy and entropy components using the support vector machine based scoring functions should be of value in the drug discovery process.

  18. Entropy–enthalpy transduction caused by conformational shifts can obscure the forces driving protein–ligand binding

    Science.gov (United States)

    Fenley, Andrew T.; Muddana, Hari S.; Gilson, Michael K.

    2012-01-01

    Molecular dynamics simulations of unprecedented duration now can provide new insights into biomolecular mechanisms. Analysis of a 1-ms molecular dynamics simulation of the small protein bovine pancreatic trypsin inhibitor reveals that its main conformations have different thermodynamic profiles and that perturbation of a single geometric variable, such as a torsion angle or interresidue distance, can select for occupancy of one or another conformational state. These results establish the basis for a mechanism that we term entropy–enthalpy transduction (EET), in which the thermodynamic character of a local perturbation, such as enthalpic binding of a small molecule, is camouflaged by the thermodynamics of a global conformational change induced by the perturbation, such as a switch into a high-entropy conformational state. It is noted that EET could occur in many systems, making measured entropies and enthalpies of folding and binding unreliable indicators of actual thermodynamic driving forces. The same mechanism might also account for the high experimental variance of measured enthalpies and entropies relative to free energies in some calorimetric studies. Finally, EET may be the physical mechanism underlying many cases of entropy–enthalpy compensation. PMID:23150595

  19. Prediction of enthalpy and entropy of solute segregation at individua grain boundaries of α-iron and ferrite steels

    Czech Academy of Sciences Publication Activity Database

    Lejček, Pavel; Hofmann, S.; Janovec, J.

    2007-01-01

    Roč. 462, - (2007), s. 76-85 ISSN 0921-5093 R&D Projects: GA ČR(CZ) GA106/05/0134 Institutional research plan: CEZ:AV0Z10100520 Keywords : segregation * grain boundaries * enthalpy/entropy relationship * α-iron * prediction Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.457, year: 2007

  20. Determining the Enthalpy of Vaporization of Salt Solutions Using the Cooling Effect of a Bubble Column Evaporator

    Science.gov (United States)

    Fan, Chao; Pashley, Richard M.

    2016-01-01

    The enthalpy of vaporization (?H[subscript vap]) of salt solutions is not easily measured, as a certain quantity of pure water has to be evaporated from a solution, at constant composition, and at a fixed temperature and pressure; then the corresponding heat input has to be measured. However, a simple bubble column evaporator (BCE) was used as a…

  1. A Reaction Zone Enthalpy Balance Model to Simulate Shock-to-Detonation Transition and Unsteady Detonation Wave Propagation

    Science.gov (United States)

    Froger, A.

    2004-07-01

    The standard models in use to simulate the reactive detonation wave propagation are not accurate in computing the transient evolutions because they focus on the shock front, not on the reaction zone where the coupling of thermodynamic and mechanic effects occurs. The model we propose is based on a new thermodynamic description of the constituents in the reaction zone, and on the use of the enthalpy balance of the chemical reaction as the energetic parameter instead of the heat of reaction. The enthalpy balance of the reaction results from the enthalpies of formation of all the chemical species involved in the reaction and is, therefore, a physical constant. The model is based on four basic assumptions: -1) the reaction zone is anevolving intimate mixture of non-reacted material and detonation products, -2) the energy released by thereaction is inherent to the detonation products alone, -3) the two constituents have the same pressure but different temperatures, -4) the specific energy released is not a constant but is related to the enthalpy balance and depends on the thermodynamic state. The model only needs the physical properties of the materials (equations of state of the constituents, chemical reaction and initiation delay), not the CJ state nor any other sub-model. When coupled with the Euler equations this thermodynamic description of the reaction zone permits us to simulate the transient evolution of an emerging detonation for any geometry (2D or 3D) or confinement structure.

  2. Molar volume, excess enthalpy, and Prigogine-Defay ratio of some silicate glasses with different (P,T) histories.

    Science.gov (United States)

    Wondraczek, Lothar; Behrens, Harald

    2007-10-21

    Structural relaxation in silicate glasses with different (p,T) histories was experimentally examined by differential scanning calorimetry and measurements of molar volume under ambient pressure. Temperature and pressure-dependent rates of changes in molar volume and generation of excess enthalpy were determined for sodium trisilicate, soda lime silicate, and sodium borosilicate (NBS) compositions. From the derived data, Prigogine-Defay ratios are calculated and discussed. Changes of excess enthalpy are governed mainly by changes in short-range structure, as is shown for NBS where boron coordination is highly sensitive to pressure. For all three glasses, it is shown how the relaxation functions that underlie volume, enthalpy, and structural relaxation decouple for changes in cooling rates and pressure of freezing, respectively. The magnitude of the divergence between enthalpy and volume may be related to differences in structural sensitivity to changes in the (p,V,T,t) space on different length scales. The findings suggest that the Prigogine-Defay ratio is related to the magnitude of the discussed decoupling effect.

  3. Entropy-enthalpy compensation at the single protein level: pH sensing in the bacterial channel OmpF

    Science.gov (United States)

    Alcaraz, Antonio; Queralt-Martín, María; Verdiá-Báguena, Carmina; Aguilella, Vicente M.; Mafé, Salvador

    2014-11-01

    The pH sensing mechanism of the OmpF channel operates via ligand modification: increasing acidity induces the replacement of cations with protons in critical binding sites decreasing the channel conductance. Aside from the change in enthalpy associated with the binding, there is also a change in the microscopic arrangements of ligands, receptors and the surrounding solvent. We show that the pH-modulation of the single channel conduction involves small free energy changes because large enthalpic and entropic contributions change in opposite ways, demonstrating an approximate enthalpy-entropy compensation for different salts and concentrations.The pH sensing mechanism of the OmpF channel operates via ligand modification: increasing acidity induces the replacement of cations with protons in critical binding sites decreasing the channel conductance. Aside from the change in enthalpy associated with the binding, there is also a change in the microscopic arrangements of ligands, receptors and the surrounding solvent. We show that the pH-modulation of the single channel conduction involves small free energy changes because large enthalpic and entropic contributions change in opposite ways, demonstrating an approximate enthalpy-entropy compensation for different salts and concentrations. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03811h

  4. Bayesian Statistical Mechanics: Entropy-Enthalpy Compensation and Universal Equation of State at the Tip of Pen

    Directory of Open Access Journals (Sweden)

    Evgeni B. Starikov

    2018-02-01

    Full Text Available This work has shown the way to put the formal statistical-mechanical basement under the hotly debated notion of enthalpy-entropy compensation. The possibility of writing down the universal equation of state based upon the statistical mechanics is discussed here.

  5. Evaluation of a self-aspirating local total enthalpy probe in a low-density arc-heated hypersonic wind tunnel

    Science.gov (United States)

    Guy, R. W.; Kantsios, A. G.

    1972-01-01

    A shock-swallowing, self-aspirating, local total enthalpy probe has been evaluated in a low density nonequilibrium, hypervelocity airstream. The probe, which incorporated an air gap to separate the internal and external cooling passages, was tested in an electric archeated wind tunnel at an average Mach number of 11.7 and an average Reynolds number per meter of 57,000. The free stream enthalpy probe data are compared with bulk calorimeter measurements of total enthalpy at the beginning of the gas expansion and with local total enthalpy inferred from a theoretical nonequilibrium gas expansion model by using free stream velocity measurements obtained from a mass flow probe. The three techniques are in relative agreement at the lower enthalpies. However, at the higher enthalpies, the enthalpy probe data lie considerably below the other data. This low data may be caused by the chemical and vibrational energy frozen in the flow not being sensed by the probe. Other problems associated with the shock-swallowing total enthalpy probe are discussed, and recommendations for improving the probe performance are presented.

  6. Impacts of the Pacific meridional mode on rainfall over the maritime continent and australia: potential for seasonal predictions

    Science.gov (United States)

    Zhang, Wei; Villarini, Gabriele; Vecchi, Gabriel A.

    2017-11-01

    This study assesses whether, the extent to which and why the Pacific Meridional Mode (PMM) modulates rainfall in Australia and the Maritime Continent. We find a statistically significant time-lagged association between March-to-May (MAM) PMM and September-to-November (SON) rainfall in the Maritime Continent and Australia. The association is largely caused by the contribution of PMM to the El Niño Southern Oscillation (ENSO). Positive (negative) MAM PMM is generally followed by El Niño (La Niña) events in the following SON and December-to-February (DJF), which then suppresses (enhances) rainfall in the Maritime Continent and Australia. The suppression (enhancement) of rainfall is closely tied to the dynamical changes of moisture flux using moisture flux potential and its divergent components. Following the positive (negative) PMM phases, there is a strong moisture flux potential sink (source) in SON over the Maritime Continent and Australia, which act to suppress (enhance) rainfall there. Using MAM PMM as a predictor for SON rainfall in the Maritime Continent and Australia, the prediction skill is comparable to the North American Multimodel Ensemble project (NMME) forecasts initialized in June over the period 1981-2014. This suggests that MAM PMM may be used as a predictor for SON rainfall in the Maritime Continent and Australia.

  7. Afganistán pos-2014: las implicaciones para la estabilidad de la periferia meridional de Rusia

    Directory of Open Access Journals (Sweden)

    Tracey German

    2015-08-01

    Full Text Available Afganistán y la amplia región de Asia central constituyen parte del «punto sensible meridional» de Rusia, un término que subraya el sentido de vulnerabilidad que siente a lo largo de la frontera del Sur. Las preocupaciones rusas en seguridad en la región se centran en la inestabilidad transfronteriza, incluyendo la proliferación del extremismo religioso y el tráfico de drogas. Moscú está inquieta por la posibilidad de un mayor deterioro en la situación interna de Afganistán tras la retirada de las fuerzas internacionales en 2014, y por lo tanto ha tomado medidas para reforzar de diversos modos la seguridad tanto de Afganistán como de sus vecinos de Asia central. Este artículo analiza los conductores de la política rusa y valora sus percepciones sobre la amenaza y seguridad en la región, centrándose en particular en las implicaciones para Rusia del retiro de la operación internacional de estabilidad (ISAF en Afganistán.

  8. Meridional patterns of inorganic nutrient limitation and co-limitation of bacterial growth in the Atlantic Ocean

    Science.gov (United States)

    Hale, Michelle S.; Li, William K. W.; Rivkin, Richard B.

    2017-11-01

    Growth of heterotrophic bacteria is generally considered to be controlled by temperature and the availability of organic substrates, however there is evidence that bacterial growth can also be limited by the concentrations or supply rate of inorganic nutrients (i.e. nitrogen, phosphorus or iron). We examined spatial and seasonal patterns of organic carbon and inorganic nutrient (N and P) limitation of bacterial growth along each of two meridional transects through the Atlantic Ocean, during contrasting seasons. Here we used nutrient bioassays to demonstrate widespread inorganic nutrient limitation and co-limitation with organic carbon in the oligotrophic temperate, tropical and subtropical ocean. There were distinct seasonal and spatial differences in the inorganic and organic nutrient limitation of bacterial growth, with inorganic nitrogen as the primary limiting nutrient in May/June, and inorganic nitrogen and organic carbon co-limiting growth in October/November. There was no evidence that the availability of inorganic phosphorus limited bacterial growth in the Southern Hemisphere. We propose that the patterns of nutrient-dependent bacterial growth reflect seasonal and spatial differences in aeolian inputs and the quality of dissolved organic matter, and that bacteria directly compete with autotrophs for inorganic nutrients in the oligotrophic regions of the World Ocean. The findings of this study have important implications for understanding the balance between the biological and microbial carbon pumps, and the modelling of the net metabolic balance of the Ocean in response to climate-driven changes in nutrient inputs.

  9. Interdecadal Change in the Relationship Between the North Pacific Oscillation and the Pacific Meridional Mode and Its Impact on ENSO

    Science.gov (United States)

    Shin, So-Jung; An, Soon-Il

    2018-02-01

    Two leading but independent modes of Northern Pacific atmospheric circulation: the North Pacific Oscillation (NPO) and the Pacific Meridional Mode (PMM), are known external triggers of the El Niño-Southern Oscillation (ENSO) by the sequential migration of sea surface temperature (SST) anomalies into the tropics possibly by means of wind-evaporation-SST (WES) feedbacks. Because of the similar roles of NPO and PMM, most previous studies have explored them with no separation. Here, we investigate their independent and combined effects in triggering ENSO, and find that when the NPO and PMM occur simultaneously during spring, ENSO or ENSO-like SST anomalies are generated during the following winter; whereas when either the NPO or PMM occur alone, ENSO events rarely occur. Furthermore, the relationship between NPO and PMM shows noticeable interdecadal variability, which is related to decadal changes in the mean upper-level jet stream over the North Pacific. Changes in the upper-level jet stream modify the location of the center of the Aleutian Low, which plays a role in bridging the NPO and PMM processes, especially when it migrates to the southwest. The period when NPO and PMM are well correlated coincides somewhat with the active ENSO period, and vice versa, indicating that a more efficient trigger due to combined NPO-PMM processes results in a higher variation of ENSO. Finally, analysis of the coupled model control simulations strongly supports our observational analysis results.

  10. On the collapse of the meridional SST gradient in the eastern tropical South Pacific during Heinrich stadial 1

    Science.gov (United States)

    Kienast, S. S.; Dubois, N.; Kienast, M.; Francois, R. H.; Hill, P. S.

    2011-12-01

    The equatorial Pacific plays a crucial role in the present-day climate system. The El Nino-Southern Oscillation (ENSO) Phenomenon , which originates from perturbations of the ocean atmosphere system in this region, affects climate and the carbon cycle worldwide. One of the factors controlling ENSO variability is the meridional temperature gradient across the equator. Here we present multiproxy records of several cores located strategically across the frontal system separating the tropical warm pool north of the equator from the cold tongue off Peru. Alkenone-based sea surface temperature (SST) reconstructions display a 50% reduction in the temperature gradient across this front during Heinrich stadial 1 (H1). This dramatic change in sea surface conditions is paralleled by a) perturbations of the marine nitrogen cycle as recorded by d15N of bulk sediment and b) a maximum in continental input as recorded by 232-thorium. While 232-thorium fluxes clearly indicate an increase in overall continental input during H1, grain- size analyses suggest that the proportion of dust-sized particles in the continental fraction did not vary significantly between the last glacial maximum, H1, and the Holocene. Implications for ocean atmosphere dynamics and comparisons to model predictions for this time period will be discussed.

  11. Initial forces values in the double-layer metal dome in case of elimination of normal and meridional imperfections of installation

    Directory of Open Access Journals (Sweden)

    Grigoryan Artem Akopovich

    2016-01-01

    Full Text Available OF INSTALLATION Computer analysis of the values of the initial forces due to force elimination of assembly errors of double-layer framed metal dome has been performed. The position errors of nodes of pair meridional ribs were considered in the normal and meridional directions at installation of the dome frame with temporary central support. For selected nodes concentrated forces were applied to eliminate the relative deviations of adjacent ribs and the resulting internal forces in the bars were registered. The values of these internal forces were compared to the forces in bars resulting from the dead load and design load. The results of the investigation are presented in the form of figures, diagrams, tables and graphs. Based on the analysis of the data obtained, conclusions are made about the influence of initial forces on the stress state of the frame of the dome.

  12. Performance analyses of a hybrid geothermal–fossil power generation system using low-enthalpy geothermal resources

    International Nuclear Information System (INIS)

    Liu, Qiang; Shang, Linlin; 2 Utilization and Reduction Technology, Tsinghua University, Beijing 100084 (China))" data-affiliation=" (Key Laboratory of Thermal Science and Power Engineering of MOE, Beijing Key Laboratory for CO2 Utilization and Reduction Technology, Tsinghua University, Beijing 100084 (China))" >Duan, Yuanyuan

    2016-01-01

    Highlights: • Geothermal energy is used to preheat the feedwater in a coal-fired power unit. • The performance of a hybrid geothermal–fossil power generation system is analyzed. • Models for both parallel and serial geothermal preheating schemes are presented. • Effects of geothermal source temperatures, distances and heat losses are analyzed. • Power increase of the hybrid system over an ORC and tipping distance are discussed. - Abstract: Low-enthalpy geothermal heat can be efficiently utilized for feedwater preheating in coal-fired power plants by replacing some of the high-grade steam that can then be used to generate more power. This study analyzes a hybrid geothermal–fossil power generation system including a supercritical 1000 MW power unit and a geothermal feedwater preheating system. This study models for parallel and serial geothermal preheating schemes and analyzes the thermodynamic performance of the hybrid geothermal–fossil power generation system for various geothermal resource temperatures. The models are used to analyze the effects of the temperature matching between the geothermal water and the feedwater, the heat losses and pumping power during the geothermal water transport and the resource distance and temperature on the power increase to improve the power generation. The serial geothermal preheating (SGP) scheme generally generates more additional power than the parallel geothermal preheating (PGP) scheme for geothermal resource temperatures of 100–130 °C, but the SGP scheme generates slightly less additional power than the PGP scheme when the feedwater is preheated to as high a temperature as possible before entering the deaerator for geothermal resource temperatures higher than 140 °C. The additional power decreases as the geothermal source distance increases since the pipeline pumping power increases and the geothermal water temperature decreases due to heat losses. More than 50% of the power decrease is due to geothermal

  13. Synthesis and characterization of meridional isomer of uns-cis-(ethylenediamine-N-N'-di-3-propionato-(S-norleucinatocobalt(III semihydrate

    Directory of Open Access Journals (Sweden)

    SRECKO R. TRIFUNOVIC

    2000-07-01

    Full Text Available The meridional geometrical isomer of uns-cis-(ethylenediamine-N-N'-di-3-propionato(S-norleucinatocobalt(III complex has been prepared by the reaction of sodium uns-cis-(ethylenediamine-N-N'-di-3-propionato(carbonatocobaltate(III with S-norleucine at 75°C. The complex was isolated choromatographically and characterized by elemental analyses, electron absorption and infrared spectroscopy.

  14. «Theater of Sorrows»: Rhetoric and Space in Francisco Romero's «Llanto Sagrado de la América Meridional»

    Directory of Open Access Journals (Sweden)

    Jorge Martín García

    2016-11-01

    Full Text Available This article aims to analyze the text entitled Llanto sagrado de la América Meridional written by the Augustinian friar Francisco Romero. The work presents a kind of spiritual mapping of american land. Therefore, the text divides the territory of the continent according to their proximity or remoteness from the true faith. Our main objective will be to examine the rhetorical mechanisms that lie behind this description of the Indian space.

  15. Overturn of the Oceasn Flow in the North Atlantic as a Trigger of Inertia Motion to Form a Meridional Ocean Circulation

    Science.gov (United States)

    Nakamura, Shigehisa

    2010-05-01

    This work is an introduction of a meridional ocean circulation. As for the zonal motions,there have been many contributions. Recent oceanographic works noticed an overturn of the ocean current in the North Atlantic. The author notices this overturn is a trigger to generate a meridional ocean circulation to have a track through the deep Atlantic, the deep circum-polar current, the deep branch flow to the Pacific between the Australian and the South America. The east part of the branch flow relates to the upwelling off Peru, and the west part relates to form a deep water in the Northwest Pacific. THe overturn of the North Atlantic suggests an outflow of the deep water and a storage of the old aged deep water in the Northwest Pacific. The storage water increase in the Northwest Pacific shoould be a trigger of the swelling up of the sea level mid Pacific to affect to the ocean front variations between the coastal waters and the ocean water. In order to keep a hydrodynamic balance on the earth, an increase of the deep water in the Pacific should flow through the Bering Sea and the Arctic Sea to get to the North Atlantic. It should be noted that a budget of the ocean water flow must be hold the condition of the water masses concservation on the earth surface. This inertia motion is maintained once induced after any natural effect or some man-made influences. At this stage, the author has to notice that there has been developed a meridional inertia path of the air particle as well as the ocean water parcel, nevertheless nobody has had pointed out this inertiamotion with a meridional path in the ocean. Air-sea interaction must be one of the main factors for driving the ocean water though the inertia motion in the global scale is more energetic. To the details, the scientists should pursue what geophysical dynamics must be developed in the future.

  16. SYSTEMATIC CENTER-TO-LIMB VARIATION IN MEASURED HELIOSEISMIC TRAVEL TIMES AND ITS EFFECT ON INFERENCES OF SOLAR INTERIOR MERIDIONAL FLOWS

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Junwei; Nagashima, Kaori; Bogart, R. S.; Kosovichev, A. G. [W. W. Hansen Experimental Physics Laboratory, Stanford University, Stanford, CA 94305-4085 (United States); Duvall, T. L. Jr. [Solar Physics Laboratory, NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States)

    2012-04-10

    We report on a systematic center-to-limb variation in measured helioseismic travel times, which must be taken into account for an accurate determination of solar interior meridional flows. The systematic variation, found in time-distance helioseismology analysis using SDO/HMI and SDO/AIA observations, is different in both travel-time magnitude and variation trend for different observables. It is not clear what causes this systematic effect. Subtracting the longitude-dependent east-west travel times, obtained along the equatorial area, from the latitude-dependent north-south travel times, obtained along the central meridian area, gives remarkably similar results for different observables. We suggest this as an effective procedure for removing the systematic center-to-limb variation. The subsurface meridional flows obtained from inversion of the corrected travel times are approximately 10 m s{sup -1} slower than those obtained without removing the systematic effect. The detected center-to-limb variation may have important implications in the derivation of meridional flows in the deep interior and needs to be better understood.

  17. Sediment 231Pa/230Th as a recorder of the rate of the Atlantic meridional overturning circulation: insights from a 2-D model

    Directory of Open Access Journals (Sweden)

    S. E. Allen

    2010-03-01

    Full Text Available A two dimensional scavenging model is used to investigate the patterns of sediment 231Pa/230Th generated by the Atlantic Meridional Overturning Circulation (AMOC and further advance the application of this proxy for ocean paleocirculation studies. The scavenging parameters and the geometry of the overturning circulation cell have been chosen so that the model generates meridional sections of dissolved 230Th and 231Pa consistent with published water column profiles and an additional 12 previously unpublished profiles measured in the North and Equatorial Atlantic. The processes that generate the meridional sections of dissolved and particulate 230Th, dissolved and particulate 231Pa, dissolved and particulate 231Pa/230Th, and sediment 231Pa/230Th are discussed in detail. The results indicate that the relationship between sediment 231Pa/230Th at any given site and the overturning circulation is very complex. They clearly show that constraining past changes in the strength and geometry of the AMOC requires an extensive data set and they suggest strategies to maximize information from a limited number of samples.

  18. Systematic Center-To-Limb Variation in Measured Helioseismic Travel Times and Its Effect on Inferences of Solar Interior Meridional Flows

    Science.gov (United States)

    Zhao, Junwei; Nagashima, Kaori; Bogart, R. S.; Kosovichev, Alexander; Duvall, T. L., Jr.

    2012-01-01

    We report on a systematic center-to-limb variation in measured helioseismic travel times, which must be taken into account for an accurate determination of solar interior meridional flows. The systematic variation, found in time-distance helioseismology analysis using SDO/HMI and SDO/AIA observations, is different in both travel-time magnitude and variation trend for different observables. It is not clear what causes this systematic effect. Subtracting the longitude-dependent east-west travel times, obtained along the equatorial area, from the latitude-dependent north-south travel times, obtained along the central meridian area, gives remarkably similar results for different observables. We suggest this as an effective procedure for removing the systematic center-to-limb variation. The subsurface meridional flows obtained from inversion of the corrected travel times are approximately 10 m s-1 slower than those obtained without removing the systematic effect. The detected center-to-limb variation may have important implications in the derivation of meridional flows in the deep interior and needs to be better understood.

  19. SYSTEMATIC CENTER-TO-LIMB VARIATION IN MEASURED HELIOSEISMIC TRAVEL TIMES AND ITS EFFECT ON INFERENCES OF SOLAR INTERIOR MERIDIONAL FLOWS

    International Nuclear Information System (INIS)

    Zhao Junwei; Nagashima, Kaori; Bogart, R. S.; Kosovichev, A. G.; Duvall, T. L. Jr.

    2012-01-01

    We report on a systematic center-to-limb variation in measured helioseismic travel times, which must be taken into account for an accurate determination of solar interior meridional flows. The systematic variation, found in time-distance helioseismology analysis using SDO/HMI and SDO/AIA observations, is different in both travel-time magnitude and variation trend for different observables. It is not clear what causes this systematic effect. Subtracting the longitude-dependent east-west travel times, obtained along the equatorial area, from the latitude-dependent north-south travel times, obtained along the central meridian area, gives remarkably similar results for different observables. We suggest this as an effective procedure for removing the systematic center-to-limb variation. The subsurface meridional flows obtained from inversion of the corrected travel times are approximately 10 m s –1 slower than those obtained without removing the systematic effect. The detected center-to-limb variation may have important implications in the derivation of meridional flows in the deep interior and needs to be better understood.

  20. Role of the meridional dipole of SSTA and associated cross-equatorial flow in the tropical eastern Pacific in terminating the 2014 El Niño development

    Science.gov (United States)

    Wu, Yi-Kai; Chen, Lin; Hong, Chi-Cherng; Li, Tim; Chen, Cheng-Ta; Wang, Lu

    2018-03-01

    In the boreal spring of 2014, the oceanic and atmospheric conditions were favorable for an El Niño's development. It was predicted that in 2014, a super El Niño or at least a regular El Niño with normal magnitude, would initiate. However, the growth rate of the sea surface temperature anomaly (SSTA) in the equatorial eastern Pacific suddenly declined in the boreal summer. The physical processes responsible for the termination of the 2014 El Niño were addressed in this study. We hypothesized that a meridional dipole of SSTA, characterized by a pronounced warm SSTA over the eastern North Pacific (ENP) and cold SSTA over the eastern South Pacific (ESP), played a crucial role in blocking the 2014 El Niño's development. The observational analysis revealed that the meridional dipole of SSTA and the relevant anomalous cross-equatorial flow in the tropical eastern Pacific, induced anomalous westward ({u^' }0) currents in the equatorial eastern Pacific, leading to negative anomalous zonal advection term (- {u^' }partial \\overline T /partial xchanges of the oceanic dynamic terms collectively caused negative SSTA tendency in the boreal summer, and thus killed off the budding 2014 El Niño. The idealized numerical experiments further confirmed that the 2014 El Niño's development could be suppressed by the meridional dipole of SSTA, and both the ENP pole and ESP pole make a contribution.

  1. NOAA/EcoFOCI Chukchi Sea ADCP Mooring time-series data, stations C1, C2, and C3, 2010-08-29 to 2012-08-22, including zonal (U) and meridional (V) current measurements (NCEI Accession 0149848)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — These Acoustic Doppler Current Profiler (ADCP) time-series data sets, consist of zonal current (U) and meridional current (V) measurements from moored instruments at...

  2. Charged de Sitter-like black holes: quintessence-dependent enthalpy and new extreme solutions

    Energy Technology Data Exchange (ETDEWEB)

    Azreg-Ainou, Mustapha [Baskent University, Faculty of Engineering, Ankara (Turkey)

    2015-01-01

    We consider Reissner-Nordstroem black holes surrounded by quintessence where both a non-extremal event horizon and a cosmological horizon exist besides an inner horizon (-1 ≤ ω < -1/3). We determine new extreme black hole solutions that generalize the Nariai horizon to asymptotically de Sitter-like solutions for any order relation between the squares of the charge q{sup 2} and the mass parameter M{sup 2} provided q{sup 2} remains smaller than some limit, which is larger than M{sup 2}. In the limit case q{sup 2} = 9ω{sup 2}M{sup 2}/(9ω{sup 2}-1), we derive the general expression of the extreme cosmo-blackhole, where the three horizons merge, and we discuss some of its properties.We also show that the endpoint of the evaporation process is independent of any order relation between q{sup 2} and M{sup 2}. The Teitelboim energy and the Padmanabhan energy are related by a nonlinear expression and are shown to correspond to different ensembles. We also determine the enthalpy H of the event horizon, as well as the effective thermodynamic volume which is the conjugate variable of the negative quintessential pressure, and show that in general the mass parameter and the Teitelboim energy are different from the enthalpy and internal energy; only in the cosmological case, that is, for Reissner-Nordstroem-de Sitter black hole we have H = M. Generalized Smarr formulas are also derived. It is concluded that the internal energy has a universal expression for all static charged black holes, with possibly a variable mass parameter, but it is not a suitable thermodynamic potential for static-black-hole thermodynamics if M is constant. It is also shown that the reverse isoperimetric inequality holds. We generalize the results to the case of the Reissner-Nordstroem-de Sitter black hole surrounded by quintessence with two physical constants yielding two thermodynamic volumes. (orig.)

  3. Accurate Gas Phase Formation Enthalpies of Alloys and Refractories Decomposition Products

    KAUST Repository

    Minenkov, Yury

    2017-01-17

    Accurate gas phase formation enthalpies, ΔHf, of metal oxides and halides are critical for the prediction of the stability of high temperature materials used in the aerospace and nuclear industries. Unfortunately, the experimental ΔHf values of these compounds in the most used databases, such as the NIST-JANAF database, are often reported with large inaccuracy, while some other ΔHf values clearly differ from the value predicted by CCSD(T) methods. To address this point, in this work we systematically predicted the ΔHf values of a series of these compounds having a group 4, 6, or 14 metal. The ΔHf values in question were derived within a composite Feller-Dixon-Peterson (FDP) scheme based protocol that combines the DLPNO-CCSD(T) enthalpy of ad hoc designed reactions and the experimental ΔHf values of few reference complexes. In agreement with other theoretical studies, we predict the ΔHf values for TiOCl2, TiOF2, GeF2, and SnF4 to be significantly different from the values tabulated in NIST-JANAF and other sources, which suggests that the tabulated experimental values are inaccurate. Similarly, the predicted ΔHf values for HfCl2, HfBr2, HfI2, MoOF4, MoCl6, WOF4, WOCl4, GeO2, SnO2, PbBr4, PbI4, and PbO2 also clearly differ from the tabulated experimental values, again suggesting large inaccuracy in the experimental values. In the case when largely different experimental values are available, we point to the value that is in better agreement with our results. We expect the ΔHf values reported in this work to be quite accurate, and thus, they might be used in thermodynamic calculations, because the effects from core correlation, relativistic effects, and basis set incompleteness were included in the DLPNO-CCSD(T) calculations. T1 and T2 values were thoroughly monitored as indicators of the quality of the reference Hartree-Fock orbitals (T1) and potential multireference character of the systems (T2).

  4. An Anthropogenic Radioisotope, Iodine 129, As A Tracer For Studying The Northern Limb of The Meridional Overturning Circulation (moc)

    Science.gov (United States)

    Gascard, J. C.; Raisbeck, G.; Yiou, F.; Sequeira, S.; Mork, K. A.

    A number of observations taken during the 1990s, seem to corroborate the fact that the northern limb of the Meridional Overturning Circulation (the so-called MOC), is undergoing large scale variability. Arctic Sea-Ice thinning, Overflows slackening, Labrador and Greenland Seas Deep Convection weakening, have recently been re- ported. Can this large scale variability be interpreted as a natural variability of the MOC or is it more related to global changes due to anthropogenic effects like green- house gases enhancing Global Warming at High Latitudes ? Iodine 129 resulting from reprocessing nuclear wastes at La Hague (France) and Sellafield (UK), has penetrated through all the various parts of the MOC from the Source: the Norwegian Coastal Current (NCC) collecting Iodine 129 from the North Sea, to the Sink: the Greenland- Iceland-Scotland Overflows and ultimately to the North Atlantic Deep Waters via the Deep Western Boundary Current. During recent years, discharges of Iodine 129 have increased drastically and peaks in Iodine 129 concentrations have already been ob- served all along the coast of Norway. In this talk, we will first present the most recent results showing the transfer of Iodine 129 through the various parts of the MOC from the NCC down to the North Atlantic Overflows (Denmark Strait), and second, explain how this results allow us to improve our understanding of the MOC system and in particular its variability. This is an important issue for improving reliability of actual numerical simulations of past, present and future behavior of the MOC, which has strong implications for climate related problems.

  5. Exceptional Shift to a Weaker Atlantic Meridional Overturning Circulation at the end of the Little Ice Age

    Science.gov (United States)

    Thornalley, D. J.; Oppo, D.; Moffa Sanchez, P.; Hall, I. R.; Keigwin, L. D.; Rose, N.; Green, K.; Pallottino, F.; Ortega, P.; Robson, J.

    2016-12-01

    Several proxy and modelling studies suggest that there may have been considerable change in the operation of the Atlantic Meridional Overturning Circulation (AMOC) during the last two millennia. Yet despite its importance for regional and global climate, the recent history of the AMOC is poorly constrained and comprehensive observational records only extend back a few decades at most. Observational data suggest that the export of large volumes of sea-ice and freshwater from the Arctic during the Great Salinity Anomaly of the late 1960s to early 1970s impacted North Atlantic circulation, and perhaps the strength of the AMOC, thus raising the possibility that more extreme events may have affected the AMOC during the pre-instrumental era. We present a suite of AMOC related proxies from high resolution marine sediment cores from the North Atlantic, spanning the last 2000 years, including proxies for both deep ocean circulation and surface ocean climate. Our results suggest that there was an exceptional shift to a weaker mode of Labrador Sea Water (LSW) formation during the late 19th century, which persisted up to the present day, notwithstanding strong decadal-scale LSW production events such as during the 1990s. Using a compilation of sites that allow the sea-surface temperature fingerprint of AMOC change to be identified, we show that the shift to weaker LSW formation was accompanied by a weakening of the combined AMOC. Preliminary data suggests that this exceptional event impacted marine ecosystems in certain locations. Based on their timing, we infer that the weakening of LSW and AMOC may have been caused by the export of sea-ice and freshwater from the Arctic during the termination of the Little Ice Age (somewhat mimicking, albeit on a smaller scale, the AMOC weakening events that accompanied the last Ice Age termination). These results have significant implications for the sensitivity of the AMOC to climate forcing, and the cause of late Holocene climate events.

  6. Predominant nonlinear atmospheric response to meridional shift of the Gulf Stream path from the WRF atmospheric model simulations

    Science.gov (United States)

    Seo, H.; Kwon, Y. O.; Joyce, T. M.

    2016-02-01

    A remarkably strong nonlinear behavior of the atmospheric circulation response to North Atlantic SST anomalies (SSTA) is revealed from a set of large-ensemble, high-resolution, and hemispheric-scale Weather Research and Forecasting (WRF) model simulations. The model is forced with the SSTA associated with meridional shift of the Gulf Stream (GS) path, constructed from a lag regression of the winter SST on a GS Index from observation. Analysis of the systematic set of experiments with SSTAs of varied amplitudes and switched signs representing various GS-shift scenarios provides unique insights into mechanism for emergence and evolution of transient and equilibrium response of atmospheric circulation to extratropical SSTA. Results show that, independent of sign of the SSTA, the equilibrium response is characterized by an anomalous trough over the North Atlantic Ocean and the Western Europe concurrent with enhanced storm track, increased rainfall, and reduced blocking days. To the north of the anomalous low, an anomalous ridge emerges over the Greenland, Iceland, and Norwegian Seas accompanied by weakened storm track, reduced rainfall and increased blocking days. This nonlinear component of the total response dominates the weak and oppositely signed linear response that is directly forced by the SSTA, yielding an anomalous ridge (trough) downstream of the warm (cold) SSTA. The amplitude of the linear response is proportional to that of the SSTA, but this is masked by the overwhelmingly strong nonlinear behavior showing no clear correspondence to the SSTA amplitude. The nonlinear pattern emerges 3-4 weeks after the model initialization in November and reaches its first peak amplitude in December/January. It appears that altered baroclinic wave activity due to the GS SSTA in November lead to low-frequency height responses in December/January through transient eddy vorticity flux convergence.

  7. Enthalpy-entropy contributions to salt and osmolyte effects on molecular-scale hydrophobic hydration and interactions.

    Science.gov (United States)

    Athawale, Manoj V; Sarupria, Sapna; Garde, Shekhar

    2008-05-08

    Salts and additives can significantly affect the strength of water-mediated interactions in solution. We present results from molecular dynamics simulations focused on the thermodynamics of hydrophobic hydration, association, and the folding-unfolding of a hydrophobic polymer in water and in aqueous solutions of NaCl and of an osmolyte trimethylamine oxide (TMAO). It is known that addition of NaCl makes the hydration of hydrophobic solutes unfavorable and, correspondingly, strengthens their association at the pair as well as the many-body level (Ghosh, T.; Kalra, A.; Garde, S. J. Phys. Chem. B 2005, 109, 642), whereas the osmolyte TMAO has an almost negligible effect on the hydrophobic hydration and association (Athawale, M. V.; Dordick, J. S.; Garde, S. Biophys. J. 2005, 89, 858). Whether these effects are enthalpic or entropic in origin is not fully known. Here we perform temperature-dependent simulations to resolve the free energy into entropy and enthalpy contributions. We find that in TMAO solutions, there is an almost precise entropy-enthalpy compensation leading to the negligible effect of TMAO on hydrophobic phenomena. In contrast, in NaCl solutions, changes in enthalpy dominate, making the salt-induced strengthening of hydrophobic interactions enthalpic in origin. The resolution of total enthalpy into solute-solvent and solvent-solvent terms further shows that enthalpy changes originate primarily from solvent-solvent energy terms. Our results are consistent with experimental data on the hydration of small hydrophobic solutes by Ben-Naim and Yaacobi (Ben-Naim, A.; Yaacobi, M. J. Phys. Chem. 1974, 78, 170). In combination with recent work by Zangi, Hagen, and Berne (Zangi, R.; Hagen, M.; Berne, B. J. J. Am. Chem. Soc. 2007, 129, 4678) and the experimental data on surface tensions of salt solutions by Matubayasi et al. (Matubayasi, N.; Matsuo, H.; Yamamoto, K.; Yamaguchi, S.; Matuzawa, A. J. Colloid Interface Sci. 1999, 209, 398), our results highlight

  8. Calibration of Axisymmetric and Quasi-1D Solvers for High Enthalpy Nozzles

    Science.gov (United States)

    Papadopoulos, P. E.; Gochberg, L. A.; Tokarcik-Polsky, S.; Venkatapathy, E.; Deiwert, G. S.; Edwards, Thomas A. (Technical Monitor)

    1994-01-01

    The proposed paper will present a numerical investigation of the flow characteristics and boundary layer development in the nozzles of high enthalpy shock tunnel facilities used for hypersonic propulsion testing. The computed flow will be validated against existing experimental data. Pitot pressure data obtained at the entrance of the test cabin will be used to validate the numerical simulations. It is necessary to accurately model the facility nozzles in order to characterize the test article flow conditions. Initially the axisymmetric nozzle flow will be computed using a Navier Stokes solver for a range of reservoir conditions. The calculated solutions will be compared and calibrated against available experimental data from the DLR HEG piston-driven shock tunnel and the 16-inch shock tunnel at NASA Ames Research Center. The Reynolds number is assumed to be high enough at the throat that the boundary layer flow is assumed turbulent at this point downstream. The real gas affects will be examined. In high Mach number facilities the boundary layer is thick. Attempts will be made to correlate the boundary layer displacement thickness. The displacement thickness correlation will be used to calibrate the quasi-1D codes NENZF and LSENS in order to provide fast and efficient tools of characterizing the facility nozzles. The calibrated quasi-1D codes will be implemented to study the effects of chemistry and the flow condition variations at the test section due to small variations in the driver gas conditions.

  9. Analysis of experimental routines of high enthalpy steam discharge in subcooled water

    Energy Technology Data Exchange (ETDEWEB)

    Pacheco, Rafael R., E-mail: Rafael.rade@ctmsp.mar.mil.br [Centro Tecnologico da Marinha em Sao Paulo (CTMSP), SP (Brazil); Andrade, Delvonei A., E-mail: delvonei@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2015-07-01

    The discharge of high enthalpy steam through safety release valves out from pressurizers in PWR's needs to be condensed in order to allow the treatment of possibly present radwaste within. The Direct Contact Condensation is used in a relief tank to achieve the condensation. Care must be taken to avoid the bypass of the steam through the subcooled water, what would increase the peak of pressure and the necessity of structural reinforcement of the relief tank. An experiment to determine the optimal set up of the relief tank components and their characteristics (type of sprinkler, level of water, volume of tank, discharge direction, pressure in the pressurizer among others) was executed in 2000, in the CTE 150 facility, in CTMSP. In a total, 144 routines varying its components and characteristics were made, although no comprehensive analysis of its results were yet made, since the mass of data was too big to be readily analyzed. In order to comprehensively analyze it, a VBA program is being made to compile and graphically represent the mass of data. The current state of this program allowed conclusions over the peak pressure, adiabatic assumption of the experiment, and the quality of the steam generated due to the discharge. (author)

  10. Calorimetric determination of the δ hydride dissolution enthalpy in Zircaloy-4

    International Nuclear Information System (INIS)

    Vizcaino, Pablo; Banchik, Abraham D.

    2003-01-01

    In this work, the dissolution enthalpy, ΔH δ→α , of the δ hydride phase in the αZr matrix in Zircaloy-4 has been determined with a differential scanning calorimeter (DSC) in two different ways: by means of a vant Hoff equation, measuring the terminal solubility temperature in dissolution, TSSd, and by direct measurement of the dissolution heat, Q δ→α , as the area between the base line and the calorimetric curve. The application of the DSC technique to the hydride dissolution heat measurements, a transformation which covers an extended temperature range, is completely original and requires a special treatment of the calorimetric curve. These measurements were done on samples, which practically cover the whole solubility range of hydrogen in αZr phase (80-640 ppm). The values obtained, 36.9 kJ/mol H and 39.3 kJ/mol H respectively, are self-consistent and in good agreement with the values of the more recent revisions, but reduces considerably the scatter of the literature data. (author)

  11. Reduction of enthalpy relaxation in gelatine films by addition of polyols.

    Science.gov (United States)

    Díaz-Calderón, Paulo; MacNaughtan, Bill; Hill, Sandra; Mitchell, John; Enrione, Javier

    2018-04-01

    The aim of this study was to evaluate the effect of plasticisers with different molecular weights (glycerol and sorbitol) on the structural relaxation kinetics of bovine gelatine films stored under the glass transition temperature (Tg). Plasticisers were tested at weight fractions of 0.0, 0.06 and 0.10. Films conditioned in environments under ∼44% relative humidity gave moisture contents (w/w) in the range 0.14-0.18. The enthalpy relaxation (ΔH) was determined using differential scanning calorimetry (DSC). Samples used had Tg values in the range 24-49 °C. After removing the thermal history (30 °C above Tg, 15 min), samples were isothermally stored at 10 °C below Tg for between 2 and 80 h. The addition of plasticisers induced a significant reduction in the rate of structural relaxation. The linearisation of ΔH by plotting against the logarithm of ageing time showed a reduction in the slope of samples plasticised with both polyols. The reduction in relaxation kinetics may be related to the ability of polyols to act as enhancers of molecular packing, as recently reported using positron spectroscopy (PALS). However, a direct correlation between the relaxation kinetics and the plasticiser's molecular weight could not be established, suggesting that this phenomenon may be governed by complex molecular gelatin-plasticiser-water interactions. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Blunt-Body Aerothermodynamic Database from High-Enthalpy CO2 Testing in an Expansion Tunnel

    Science.gov (United States)

    Hollis, Brian R.; Prabhu, Dinesh K.; Maclean, Matthew; Dufrene, Aaron

    2016-01-01

    An extensive database of heating, pressure, and flow field measurements on a 70-deg sphere-cone blunt body geometry in high-enthalpy, CO2 flow has been generated through testing in an expansion tunnel. This database is intended to support development and validation of computational tools and methods to be employed in the design of future Mars missions. The test was conducted in an expansion tunnel in order to avoid uncertainties in the definition of free stream conditions noted in previous studies performed in reflected shock tunnels. Data were obtained across a wide range of test velocity/density conditions that produced various physical phenomena of interest, including laminar and transitional/turbulent boundary layers, non-reacting to completely dissociated post-shock gas composition and shock-layer radiation. Flow field computations were performed at the test conditions and comparisons were made with the experimental data. Based on these comparisons, it is recommended that computational uncertainties on surface heating and pressure, for laminar, reacting-gas environments can be reduced to +/-10% and +/-5%, respectively. However, for flows with turbulence and shock-layer radiation, there were not sufficient validation-quality data obtained in this study to make any conclusions with respect to uncertainties, which highlights the need for further research in these areas.

  13. Discussion of enthalpy, entropy and free energy of formation of GaN

    Science.gov (United States)

    Jacob, K. T.; Rajitha, G.

    2009-07-01

    Presented in this letter is a critical discussion of a recent paper on experimental investigation of the enthalpy, entropy and free energy of formation of gallium nitride (GaN) published in this journal [T.J. Peshek, J.C. Angus, K. Kash, J. Cryst. Growth 311 (2008) 185-189]. It is shown that the experimental technique employed detects neither the equilibrium partial pressure of N 2 corresponding to the equilibrium between Ga and GaN at fixed temperatures nor the equilibrium temperature at constant pressure of N 2. The results of Peshek et al. are discussed in the light of other information on the Gibbs energy of formation available in the literature. Entropy of GaN is derived from heat-capacity measurements. Based on a critical analysis of all thermodynamic information now available, a set of optimized parameters is identified and a table of thermodynamic data for GaN developed from 298.15 to 1400 K.

  14. Molar excess enthalpies at T = 298.15 K for (1-alkanol + dibutylether) systems

    Energy Technology Data Exchange (ETDEWEB)

    Mozo, Ismael; Garcia De La Fuente, Isaias [G.E.T.E.F., Departamento de Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, 47071 Valladolid (Spain); Gonzalez, Juan Antonio, E-mail: jagl@termo.uva.e [G.E.T.E.F., Departamento de Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, 47071 Valladolid (Spain); Cobos, Jose Carlos [G.E.T.E.F., Departamento de Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, 47071 Valladolid (Spain)

    2010-01-15

    Molar excess enthalpies, H{sub m}{sup E}, at T = 298.15 K and atmospheric pressure have been measured using a microcalorimeter Tian-Calvet for the (methanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, or 1-decanol + dibutylether) systems. Experimental results have been compared with those obtained from the ERAS, DISQUAC, and Dortmund UNIFAC models. DISQUAC and ERAS yield similar H{sub m}{sup E}, results. Larger differences between experimental and calculated H{sub m}{sup E}, values are obtained from UNIFAC. ERAS represents quite accurately the excess molar volumes, V{sub m}{sup E}, of these systems. The excess molar internal energy at constant volume, U{sub V,m}{sup E}, is nearly constant for the solutions with the longer 1-alkanols. This points out that the different interactional contributions to this magnitude are counterbalanced. Interactions between unlike molecules are stronger in methanol systems. The same behaviour is observed in mixtures with dipropylether.

  15. Hydration of lysozyme: the protein-protein interface and the enthalpy-entropy compensation.

    Science.gov (United States)

    Kocherbitov, Vitaly; Arnebrant, Thomas

    2010-03-16

    Water sorption isotherms of proteins are usually interpreted with such models as BET or GAB that imply the formation of multilayers at solid-gas interface. However, this approach is not applicable to globular proteins such as humid lysozyme where a solid-gas interface does not exist. Another popular approach is the D'Arcy-Watt model, where besides the formation of multilayers the heterogeneity of energies of sorption sites of proteins is taken into account. Here we present sorption calorimetric data on the hydration of lysozyme that confirms the existence of the heterogeneity. The magnitude of the heterogeneity is, however, lower than one can expect on the basis of the existence of a solid-gas interface. Moreover, the calorimetric data show a strong enthalpy-entropy compensation that leads to almost constant effective free energy of hydration in the activity range normally used for fitting the data to sorption models. This allows the use of the Langmuir equation for the fitting of the initial part of the sorption isotherm of lysozyme. Assuming the formation of a monolayer of water at the protein-protein interface, one can estimate the size of the lysozyme molecules from the sorption isotherm. The result of this estimation is in good agreement with the structural data on lysozyme, which supports the presented approach.

  16. A Multichannel Calorimetric Simultaneous Assay Platform Using a Microampere Constant-Current Looped Enthalpy Sensor Array.

    Science.gov (United States)

    Wei, Hsien-Chin; Huang, Su-Hua; Jiang, Joe-Air; Lee, Yeun-Chung

    2017-02-04

    Calorimetric biochemical measurements offer various advantages such as low waste, low cost, low sample consumption, short operating time, and labor-savings. Multichannel calorimeters can enhance the possibility of performing higher-throughput biochemical measurements. An enthalpy sensor (ES) array is a key device in multichannel calorimeters. Most ES arrays use Wheatstone bridge amplifiers to condition the sensor signals, but such an approach is only suitable for null detection and low resistance sensors. To overcome these limitations, we have developed a multichannel calorimetric simultaneous assay (MCSA) platform. An adjustable microampere constant-current (AMCC) source was designed for exciting the ES array using a microampere current loop measurement circuit topology. The MCSA platform comprises a measurement unit, which contains a multichannel calorimeter and an automatic simultaneous injector, and a signal processing unit, which contains multiple ES signal conditioners and a data processor. This study focused on the construction of the MCSA platform; in particular, construction of the measurement circuit and calorimeter array in a single block. The performance of the platform, including current stability, temperature sensitivity and heat sensitivity, was evaluated. The sensor response time and calorimeter constants were given. The capability of the platform to detect relative enzyme activity was also demonstrated. The experimental results show that the proposed MCSA is a flexible and powerful biochemical measurement device with higher throughput than existing alternatives.

  17. Entropy-enthalpy compensation: Role and ramifications in biomolecular ligand recognition and design

    Science.gov (United States)

    Chodera, John D.; Mobley, David L.

    2014-01-01

    Recent calorimetric studies of small molecule interactions with biomolecular targets have generated renewed interest in the phenomenon of entropy-enthalpy compensation. In these studies, entropic and enthalpic contributions to binding are observed to vary substantially and in an opposing manner as the ligand or protein is modified while the binding free energy varies little. In severe examples, engineered enthalpic gains can lead to completely compensating entropic penalties, frustrating ligand design. Here, we examine the evidence for compensation, as well as its potential origins, prevalence, severity, and ramifications for ligand engineering. We find the evidence for severe compensation to be weak in light of the large magnitude of and correlation between errors in experimental measurements of entropic and enthalpic contributions to binding, though a limited form of compensation may be common. Given the difficulty of predicting or measuring entropic and enthalpic changes to useful precision, or using this information in design, we recommend ligand engineering efforts instead focus on computational and experimental methodologies to directly assess changes in binding free energy. PMID:23654303

  18. Balance between hydration enthalpy and entropy is important for ice binding surfaces in Antifreeze Proteins.

    Science.gov (United States)

    Schauperl, Michael; Podewitz, Maren; Ortner, Teresa S; Waibl, Franz; Thoeny, Alexander; Loerting, Thomas; Liedl, Klaus R

    2017-09-19

    Antifreeze Proteins (AFPs) inhibit the growth of an ice crystal by binding to it. The detailed binding mechanism is, however, still not fully understood. We investigated three AFPs using Molecular Dynamics simulations in combination with Grid Inhomogeneous Solvation Theory, exploring their hydration thermodynamics. The observed enthalpic and entropic differences between the ice-binding sites and the inactive surface reveal key properties essential for proteins in order to bind ice: While entropic contributions are similar for all sites, the enthalpic gain for all ice-binding sites is lower than for the rest of the protein surface. In contrast to most of the recently published studies, our analyses show that enthalpic interactions are as important as an ice-like pre-ordering. Based on these observations, we propose a new, thermodynamically more refined mechanism of the ice recognition process showing that the appropriate balance between entropy and enthalpy facilitates ice-binding of proteins. Especially, high enthalpic interactions between the protein surface and water can hinder the ice-binding activity.

  19. Enthalpy-Based Thermal Evolution of Loops: III. Comparison of Zero-Dimensional Models

    Science.gov (United States)

    Cargill, P. J.; Bradshaw, Stephen J.; Klimchuk, James A.

    2012-01-01

    Zero dimensional (0D) hydrodynamic models, provide a simple and quick way to study the thermal evolution of coronal loops subjected to time-dependent heating. This paper presents a comparison of a number of 0D models that have been published in the past and is intended to provide a guide for those interested in either using the old models or developing new ones. The principal difference between the models is the way the exchange of mass and energy between corona, transition region and chromosphere is treated, as plasma cycles into and out of a loop during a heating-cooling cycle. It is shown that models based on the principles of mass and energy conservation can give satisfactory results at some, or, in the case of the Enthalpy Based Thermal Evolution of Loops (EBTEL) model, all stages of the loop evolution. Empirical models can lead to low coronal densities, spurious delays between the peak density and temperature, and, for short heating pulses, overly short loop lifetimes.

  20. Zinc bioavailability from whey. Enthalpy-entropy compensation in protein binding.

    Science.gov (United States)

    Tang, Ning; Skibsted, Leif H

    2016-11-01

    Zinc amino acid or peptide complexes improve zinc absorption, however, the thermodynamics behind the interaction between zinc ion and these potential ligands is not well characterized. Therefore, binding of zinc to amino acids, peptides and whey proteins were investigated by isothermal titration calorimetry to provide useful information for improving zinc bioavailability which is lowered by many food components like phytate. Zinc binding to lactoferrin and to bovine serum albumin was found exothermic with ∆H=-100kJ/mol and -30kJ/mol, respectively, in aqueous 0.16M NaCl of pH7.4 at 25°C by isothermal titration calorimetry, while binding to α-lactalbumin and β-lactoglobulin was slightly endothermic. Still the binding constant was for all four proteins found to have a value around 2×10 5 L/mol indicating enthalpy-entropy compensation as also confirmed for zinc binding to amino acids with cysteine being enthalpically favored, while serineenthalpy-entropy compensation makes whey proteins more homogeneous as zinc vehicles counteracting concentration fluctuation and precipitation of zinc. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. On the Possibility of Calculating Entropy, Free Energy, and Enthalpy of Vitreous Substances

    Directory of Open Access Journals (Sweden)

    Sergei V. Nemilov

    2018-03-01

    Full Text Available A critical analysis for the arguments in support of, and against, the traditional approach to thermodynamics of vitreous state is provided. In this approach one presumes that there is a continuous variation of the entropy in the glass-liquid transition temperature range, or a “continuous entropy approach” towards 0 K which produces a positive value of the entropy at T → 0 K. I find that arguments given against this traditional approach use a different understanding of the thermodynamics of glass transition on cooling a liquid, because it suggests a discontinuity or “entropy loss approach” in the variation of entropy in the glass-liquid transition range. That is based on: (1 an unjustifiable use of the classical Boltzmann statistics for interpreting the value of entropy at absolute zero; (2 the rejection of thermodynamic analysis of systems with broken ergodicity, even though the possibility of analogous analysis was proposed already by Gibbs; (3 the possibility of a finite change in entropy of a system without absorption or release of heat; and, (4 describing the thermodynamic properties of glasses in the framework of functions, instead of functionals. The last one is necessary because for glasses the entropy and enthalpy are not functions of the state, but functionals, as defined by Gibbs’ in his classification.

  2. A Multichannel Calorimetric Simultaneous Assay Platform Using a Microampere Constant-Current Looped Enthalpy Sensor Array

    Directory of Open Access Journals (Sweden)

    Hsien-Chin Wei

    2017-02-01

    Full Text Available Calorimetric biochemical measurements offer various advantages such as low waste, low cost, low sample consumption, short operating time, and labor-savings. Multichannel calorimeters can enhance the possibility of performing higher-throughput biochemical measurements. An enthalpy sensor (ES array is a key device in multichannel calorimeters. Most ES arrays use Wheatstone bridge amplifiers to condition the sensor signals, but such an approach is only suitable for null detection and low resistance sensors. To overcome these limitations, we have developed a multichannel calorimetric simultaneous assay (MCSA platform. An adjustable microampere constant-current (AMCC source was designed for exciting the ES array using a microampere current loop measurement circuit topology. The MCSA platform comprises a measurement unit, which contains a multichannel calorimeter and an automatic simultaneous injector, and a signal processing unit, which contains multiple ES signal conditioners and a data processor. This study focused on the construction of the MCSA platform; in particular, construction of the measurement circuit and calorimeter array in a single block. The performance of the platform, including current stability, temperature sensitivity and heat sensitivity, was evaluated. The sensor response time and calorimeter constants were given. The capability of the platform to detect relative enzyme activity was also demonstrated. The experimental results show that the proposed MCSA is a flexible and powerful biochemical measurement device with higher throughput than existing alternatives.

  3. The Enthalpy of Decomposition of Hydrogen Peroxide: A General Chemistry Calorimetry Experiment

    Science.gov (United States)

    Marzzacco, Charles J.

    1999-11-01

    A calorimetry experiment involving the catalytic decomposition of aqueous hydrogen peroxide is presented. The experiment is simple, inexpensive, and colorful. In its simplest form, it can be performed in less than one hour; therefore, it is quite suitable for high school labs, which often have time restrictions. The chemicals required are household or commercial 3% H2O2(aq) and 0.50 M Fe(NO3)3(aq). Styrofoam cup calorimeters and thermometers with a range from 20 to 50 oC are also required. Ideally, the thermometers should be precise to 0.01 oC. The temperature of the H2O2 solution is monitored before and after the Fe(NO3)3 catalyst is added. The addition of the catalyst results in a color change and the evolution of heat and bubbles of oxygen. At the conclusion of the reaction, the color of the reaction mixture returns to that of the original Fe(NO3)3 solution. The heat change for the reaction is determined from the temperature change, the specific heat of the solution, and the calorimeter constant. The experimental enthalpy change for the reaction is in excellent agreement with the literature value.

  4. Evaluating the Capabilities of Soil Enthalpy, Soil Moisture and Soil Temperature in Predicting Seasonal Precipitation

    Science.gov (United States)

    Zhao, Changyu; Chen, Haishan; Sun, Shanlei

    2018-04-01

    Soil enthalpy ( H) contains the combined effects of both soil moisture ( w) and soil temperature ( T) in the land surface hydrothermal process. In this study, the sensitivities of H to w and T are investigated using the multi-linear regression method. Results indicate that T generally makes positive contributions to H, while w exhibits different (positive or negative) impacts due to soil ice effects. For example, w negatively contributes to H if soil contains more ice; however, after soil ice melts, w exerts positive contributions. In particular, due to lower w interannual variabilities in the deep soil layer (i.e., the fifth layer), H is more sensitive to T than to w. Moreover, to compare the potential capabilities of H, w and T in precipitation ( P) prediction, the Huanghe-Huaihe Basin (HHB) and Southeast China (SEC), with similar sensitivities of H to w and T, are selected. Analyses show that, despite similar spatial distributions of H-P and T-P correlation coefficients, the former values are always higher than the latter ones. Furthermore, H provides the most effective signals for P prediction over HHB and SEC, i.e., a significant leading correlation between May H and early summer (June) P. In summary, H, which integrates the effects of T and w as an independent variable, has greater capabilities in monitoring land surface heating and improving seasonal P prediction relative to individual land surface factors (e.g., T and w).

  5. Excess enthalpies and (vapour + liquid) equilibrium data for the binary mixtures of dimethylsulphoxide with ketones

    International Nuclear Information System (INIS)

    Radhamma, M.; Venkatesu, P.; Rao, M.V. Prabhakara; Prasad, D.H.L.

    2007-01-01

    Excess enthalpies (H E ), at ambient pressure and T = 298.15 K, have been measured by using a solution calorimeter for the binary liquid mixtures of dimethyl sulphoxide (DMSO) with ketones, as a function of composition. The ketones chosen in the present investigation were methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone (CH). The H E values are positive over the entire composition range for the three binary mixtures. Furthermore, the (vapour + liquid) equilibrium (VLE) was measured at 715 Torr for these mixtures, of different compositions, with the help of Swietoslawski-ebulliometer. The experimental temperature-mole fraction (t-x) data were used to compute Wilson parameters and then used to calculate the equilibrium vapour-phase compositions as well as the theoretical points for these binary mixtures. These Wilson parameters are used to calculate activity coefficients (γ) and these in turn to calculate excess Gibbs free energy (G E ). The intermolecular interactions and structural effects were analyzed on the basis of the measured and derived properties

  6. Enthalpy of mixing of liquid Ni-Zr and Cu-Ni-Zr alloys

    International Nuclear Information System (INIS)

    Witusiewicz, V.T.; Sommer, F.

    2000-01-01

    Since the Al-Cu-Ni-Zr system is a basis for the production of bulk amorphous materials by rapid solidification techniques from the liquid state, it is of great scientific interest to determine the partial and the integral thermodynamic functions of liquid and undercooled liquid alloys. Such data, as was pointed out previously, are important in order to understand their extremely good glass-forming ability in multicomponent metallic systems as well as for processing improvements. In order to measure the thermodynamic properties of the Al-Cu-Ni-Zr quaternary, it is necessary to have reliable thermochemical data for its constituent canaries and ternaries first. In a series of articles, the authors have reported in detail the thermodynamic properties of liquid Al-Cu, Al-Ni, Cu-Ni, Cu-Zr, Al-Zr, Al-Cu-Ni, and Al-Cu-Zr alloys. This article deals with the direct calorimetric measurements of the partial and the integral enthalpies of mixing of liquid Ni-Zr and Cu-Ni-Zr alloys and the heat capacity of liquid Ni 26 Zr 74 . In a subsequent article, the authors will present similar data for the liquid ternary Al-Ni-Zr and for the liquid quaternary Al-Cu-Ni-Zr alloys

  7. Direct calorimetric measurement of enthalpy of adsorption of carbon dioxide on CD-MOF-2, a green metal-organic framework.

    Science.gov (United States)

    Wu, Di; Gassensmith, Jeremiah J; Gouvêa, Douglas; Ushakov, Sergey; Stoddart, J Fraser; Navrotsky, Alexandra

    2013-05-08

    The enthalpy of adsorption of CO2 on an environmentally friendly metal-organic framework, CD-MOF-2, has been determined directly for the first time using adsorption calorimetry at 25 °C. This calorimetric methodology provides a much more accurate and model-independent measurement of adsorption enthalpy than that obtained by calculation from the adsorption isotherms, especially for systems showing complex and strongly exothermic adsorption behavior. The differential enthalpy of CO2 adsorption shows enthalpy values in line with chemisorption behavior. At near-zero coverage, an irreversible binding event with an enthalpy of -113.5 kJ/mol CO2 is observed, which is followed by a reversible -65.4 kJ/mol binding event. These enthalpies are assigned to adsorption on more and less reactive hydroxyl groups, respectively. Further, a second plateau shows an enthalpy of -40.1 kJ/mol and is indicative of physisorbed CO2. The calorimetric data confirm the presence of at least two energetically distinct binding sites for chemisorbed CO2 on CD-MOF-2.

  8. Evaluation of the Gibbs Free Energy Changes and Melting Temperatures of DNA/DNA Duplexes Using Hybridization Enthalpy Calculated by Molecular Dynamics Simulation.

    Science.gov (United States)

    Lomzov, Alexander A; Vorobjev, Yury N; Pyshnyi, Dmitrii V

    2015-12-10

    A molecular dynamics simulation approach was applied for the prediction of the thermal stability of oligonucleotide duplexes. It was shown that the enthalpy of the DNA/DNA complex formation could be calculated using this approach. We have studied the influence of various simulation parameters on the secondary structure and the hybridization enthalpy value of Dickerson-Drew dodecamer. The optimal simulation parameters for the most reliable prediction of the enthalpy values were determined. The thermodynamic parameters (enthalpy and entropy changes) of a duplex formation were obtained experimentally for 305 oligonucleotides of various lengths and GC-content. The resulting database was studied with molecular dynamics (MD) simulation using the optimized simulation parameters. Gibbs free energy changes and the melting temperatures were evaluated using the experimental correlation between enthalpy and entropy changes of the duplex formation and the enthalpy values calculated by the MD simulation. The average errors in the predictions of enthalpy, the Gibbs free energy change, and the melting temperature of oligonucleotide complexes were 11%, 10%, and 4.4 °C, respectively. We have shown that the molecular dynamics simulation gives a possibility to calculate the thermal stability of native DNA/DNA complexes a priori with an unexpectedly high accuracy.

  9. Parameter optimization for surface flux transport models

    Science.gov (United States)

    Whitbread, T.; Yeates, A. R.; Muñoz-Jaramillo, A.; Petrie, G. J. D.

    2017-11-01

    Accurate prediction of solar activity calls for precise calibration of solar cycle models. Consequently we aim to find optimal parameters for models which describe the physical processes on the solar surface, which in turn act as proxies for what occurs in the interior and provide source terms for coronal models. We use a genetic algorithm to optimize surface flux transport models using National Solar Observatory (NSO) magnetogram data for Solar Cycle 23. This is applied to both a 1D model that inserts new magnetic flux in the form of idealized bipolar magnetic regions, and also to a 2D model that assimilates specific shapes of real active regions. The genetic algorithm searches for parameter sets (meridional flow speed and profile, supergranular diffusivity, initial magnetic field, and radial decay time) that produce the best fit between observed and simulated butterfly diagrams, weighted by a latitude-dependent error structure which reflects uncertainty in observations. Due to the easily adaptable nature of the 2D model, the optimization process is repeated for Cycles 21, 22, and 24 in order to analyse cycle-to-cycle variation of the optimal solution. We find that the ranges and optimal solutions for the various regimes are in reasonable agreement with results from the literature, both theoretical and observational. The optimal meridional flow profiles for each regime are almost entirely within observational bounds determined by magnetic feature tracking, with the 2D model being able to accommodate the mean observed profile more successfully. Differences between models appear to be important in deciding values for the diffusive and decay terms. In like fashion, differences in the behaviours of different solar cycles lead to contrasts in parameters defining the meridional flow and initial field strength.

  10. Optimization of the exploitation system of a low enthalpy geothermal aquifer with zones of different transmissivities and temperatures

    International Nuclear Information System (INIS)

    Tselepidou, K.; Katsifarakis, K.L.

    2010-01-01

    Market penetration of renewable energy sources, such as geothermal energy, could be promoted even by small cost reductions, achieved through improved development design. This paper deals with optimization of the exploitation system of a low enthalpy geothermal aquifer, by means of the method of genetic algorithms, which has been successfully used in similar problems of groundwater resources management. With respect to water flow, the aquifer consists of two zones of different transmissivities, while from the thermal point of view it may bear any number of zones with different temperatures. The optimization process comprises the annual pumping cost of the required flow and the amortization cost of the pipe network, which carries the hot water from the wells to a central water tank, situated at the border of the geothermal field. Results show that application of the proposed methodology allows better planning of low enthalpy geothermal heating systems, which may be crucial in cases of marginal financial viability. (author)

  11. Prediction of enthalpy of fusion of pure compounds using an Artificial Neural Network-Group Contribution method

    Energy Technology Data Exchange (ETDEWEB)

    Gharagheizi, Farhad, E-mail: fghara@ut.ac.ir [Saman Energy Giti Co., Postal Code 3331619636,Tehran (Iran, Islamic Republic of); Salehi, Gholam Reza [Islamic Azad University Nowshahr Branch, Nowshahr (Iran, Islamic Republic of)

    2011-07-10

    Highlights: {yields} An Artificial Neural Network-Group Contribution method is presented for prediction of enthalpy of fusion of pure compounds at their normal melting point. {yields} Validity of the model is confirmed using a large evaluated data set containing 4157 pure compounds. {yields} The average percent error of the model is equal to 2.65% in comparison with the experimental data. - Abstract: In this work, the Artificial Neural Network-Group Contribution (ANN-GC) method is applied to estimate the enthalpy of fusion of pure chemical compounds at their normal melting point. 4157 pure compounds from various chemical families are investigated to propose a comprehensive and predictive model. The obtained results show the Squared Correlation Coefficient (R{sup 2}) of 0.999, Root Mean Square Error of 0.82 kJ/mol, and average absolute deviation lower than 2.65% for the estimated properties from existing experimental values.

  12. Thermodynamic study of rhodamine 123-calf thymus DNA interaction: determination of calorimetric enthalpy by optical melting study.

    Science.gov (United States)

    Masum, Abdulla Al; Chakraborty, Maharudra; Pandya, Prateek; Halder, Umesh Chandra; Islam, Md Maidul; Mukhopadhyay, Subrata

    2014-11-20

    In this paper, the interaction of rhodamine123 (R123) with calf thymus DNA has been studied using molecular modeling and other biophysical methods like UV-vis spectroscopy, fluoremetry, optical melting, isothermal titration calorimetry, and circular dichroic studies. Results showed that the binding energy is about -6 to -8 kcal/mol, and the binding process is favored by both negative enthalpy change and positive entropy change. A new method to determine different thermodynamic properties like calorimetric enthalpy and heat capacity change has been introduced in this paper. The obtained data has been crossed-checked by other methods. After dissecting the free-energy contribution, it was observed that the binding was favored by both negative hydrophobic free energy and negative molecular free energy which compensated for the positive free energies due to the conformational change loss of rotational and transitional freedom of the DNA helix.

  13. Non-equilibrium theory employing enthalpy-based equation of state for binary solid and porous mixtures

    Science.gov (United States)

    Nayak, B.; Menon, S. V. G.

    2018-03-01

    A generalized enthalpy-based equation of state, which includes thermal electron excitations and non-equilibrium thermal energies, is formulated for binary solid and porous mixtures. Our approach gives rise to an extra contribution to mixture volume, in addition to those corresponding to average mixture parameters. This excess term involves the difference of thermal enthalpies of the two components, which depend on their individual temperatures. We propose to use the Hugoniot of the components to compute non-equilibrium temperatures in the mixture. These are then compared with the average temperature obtained from the mixture Hugoniot, thereby giving an estimate of non-equilibrium effects. The Birch-Murnaghan model for the zero-temperature isotherm and a linear thermal model are then used for applying the method to several mixtures, including one porous case. Comparison with experimental data on the pressure-volume Hugoniot and shock speed versus particle speed shows good agreement.

  14. Heat flux and shock shape measurements on an Aeroassist Flight Experiment model in a high enthalpy free piston shock tunnel

    Science.gov (United States)

    Gai, S. L.; Mudford, N. R.; Hackett, C.

    1992-01-01

    This paper describes measurements of heat flux and shock shapes made on a 2.08 percent scale model of the proposed Aeroassist Flight Experiment model in a high enthalpy free piston shock tunnel T3 at the Australian National University in Canberra, Australia. The enthalpy and Reynolds number range covered were 7.5 MJ/kg to 20 MJ/kg and 150,000 to 270,000 per meter respectively. The test Mach number varied between 7.5 and 8. Two test gases, air and nitrogen, were used and the model angle of attack varied from -10 deg to +10 deg to the free stream. The results are discussed and compared to the Mach 10 cold hypersonic air data as obtained in the Langley 31 inch Mach 10 Facility as well as the perfect gas CFD calculations of NASA LaRC.

  15. Artificial neural network approaches for the sorption isotherms, enthalpy and entropy of heat sorption of two types block rubber products

    Directory of Open Access Journals (Sweden)

    Yutthana Tirawanichakul

    2013-02-01

    Full Text Available Knowledge of the temperature and relative humidity (or water activity dependence of moisture sorption phenomenaof agro-industrial products provides valuable information about changes related to the thermodynamics of the system. Thusthe moisture sorption characteristics in terms of equilibrium moisture contents (EMC, enthalpy and entropy of heat sorptionof natural rubber (NR for producing STR 20 and skim block rubber were investigated. Simulation modeling of water sorptionisotherms was performed using the 10 non-linear regression EMC models and the multilayer artificial neural network (ANNapproach. The results showed that the predicted EMC results using the modified Oswin model was the best fitting model forboth NR samples. However, the predicted values of ANN model were more accurate than those predicted results using nonlinear regression method. Finally, enthalpy and entropy of heat sorption for both NR samples were evaluated by applying theClausius-Clapeyron equation showing as the negative exponential function of moisture content.

  16. Interannual Variation of Seasonal Changes of Precipitation and Moisture Transport in the Western North Pacific

    OpenAIRE

    Miki, HATTORI; Kazuhisa, TSUBOKI; Takao, TAKEDA; Hydrospheric Atmospheric Research Center, Nagoya University; Hydrospheric Atmospheric Research Center, Nagoya University; Hydrospheric Atmospheric Research Center, Nagoya University

    2005-01-01

    Interannual variation of seasonal changes of precipitation and moisture transport in the western North Pacific from June to August is studied using global monthly precipitation data, and NCEP-NCAR (National Center for Environmental Prediction-National Center for Atmospheric Research) reanalysis for 20 years from 1979 to 1998. According to the meridional shift of the intense precipitation area and precipitation amounts in June and August to the east of the Philippines, the seasonal changes of ...

  17. A thermodynamic study of glucose and related oligomers in aqueous solution: Vapor pressures and enthalpies of mixing

    DEFF Research Database (Denmark)

    Cooke, S.A.; Jonsdottir, Svava Osk; Westh, Peter

    2002-01-01

    Vapor pressures above aqueous solutions of glucose and maltose at both 298.06 K and 317.99 K and vapor pressures above aqueous solutions of cellobiose, maltotriose, maltotetraose, and maltopentaose at 317.99 K have been measured. The excess enthalpies have been recorded for all of the above-menti...... in aqueous solution. This so-called transference principle is found to be of interest in furthering the discussion concerning the applicability of lattice-based models for solution theory....

  18. Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes

    KAUST Repository

    Minenkov, Yury

    2015-08-27

    The performance of the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method has been tested to reproduce the experimental gas phase ligand dissociation enthalpy in a series of Cu+, Ag+ and Au+ complexes. For 33 Cu+ - non-covalent ligand dissociation enthalpies all-electron calculations with the same method result in MUE below 2.2 kcal/mol, although a MSE of 1.4 kcal/mol indicates systematic underestimation of the experimental values. Inclusion of scalar relativistic effects for Cu either via effective core potential (ECP) or Douglass-Kroll-Hess Hamiltonian, reduces the MUE below 1.7 kcal/mol and the MSE to -1.0 kcal/mol. For 24 Ag+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) method results in a mean unsigned error (MUE) below 2.1 kcal/mol and vanishing mean signed error (MSE). For 15 Au+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) methods provides larger MUE and MSE, equal to 3.2 and 1.7 kcal/mol, which might be related to poor precision of the experimental measurements. Overall, for the combined dataset of 72 coinage metal ion complexes DLPNO-CCSD(T) results in a MUE below 2.2 kcal/mol and an almost vanishing MSE. As for a comparison with computationally cheaper density functional theory (DFT) methods, the routinely used M06 functional results in MUE and MSE equal to 3.6 and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms.

  19. Theory of the temperature dependence of positron bulk lifetimes-implications for vacancy formation enthalpy measurements via positron experiments

    International Nuclear Information System (INIS)

    Tam, S.W.; Sinha, S.K.; Siegel, R.W.

    1977-02-01

    Temperature dependent effects, which may have a bearing on determinations of vacancy formation enthalpies in metals by positron annihilation, have been observed in certain metals. These effects have been observed to occur both at temperatures below those at which positron annihilation is most sensitive to equilibrium vacancies and at temperatures well within the vacancy-sensitive region. The effect of thermal lattice displacements on positron lifetimes in metals was investigated to help understand these phenomena

  20. Artificial neural network approaches for the sorption isotherms, enthalpy and entropy of heat sorption of two types block rubber products

    OpenAIRE

    Yutthana Tirawanichakul; Jutarut Tasara; Supawan Tirawanichakul

    2013-01-01

    Knowledge of the temperature and relative humidity (or water activity) dependence of moisture sorption phenomenaof agro-industrial products provides valuable information about changes related to the thermodynamics of the system. Thusthe moisture sorption characteristics in terms of equilibrium moisture contents (EMC), enthalpy and entropy of heat sorptionof natural rubber (NR) for producing STR 20 and skim block rubber were investigated. Simulation modeling of water sorptionisotherms was perf...