Partial molar properties of magnesium base binary thermal energy storage systems
Partial molar properties of magnesium base binary thermal energy storage systems
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Partial molar properties of magnesium base binary thermal energy storage systems
Partial molar free energies, enthalpies, and entropies of carbon dissolved in solid molybdenum, tungsten, niobium, and tantalum
The objective of this work was to obtain a validated equation of state for hydrazine and monomethylhydrazine (MMH) and use this equation to calculate thermodynamic properties. The approach was based on using both reliable critical property values and a value of the acentric factor in the Soave Redlich Kwong and the Peng Robinson model equations of state. These equations were validated by comparing calculated molar volumes for phase equilibrium with published experimental values and comparing calculated vapor pressures with published experimental values over the temperature range appropriate for the corresponding state equations. The equation of state giving the best results was used to calculate enthalpy and entropy departure functions and fugacity values. Additional thermodynamic property calculations were performed to produce partial Mollier diagrams and thermodynamic properties containing internal energy, enthalpy, and entropy values for hydrazine and MMH. The analyses of systems in which either adiabatic or near-adiabatic compression of liquid or vapor hydrazine or low velocity detonations occur require a validated equation of state for representing occurring molar volumes and for energy calculations. Other calculations for thermodynamic properties of hydrazine are available, but the values are for a strict ideal gas state. This work characterized destructive events using hydrazine by calculating for isentropic compression temperatures. The final temperatures were calculated and compared using the ideal and real gas fluid equations of state.
The laboratory-measured viscosities of liquid mixtures representative of the variety of cryovolcanic substances of the icy satellites are presently noted to be much greater than could be expected on the assumption that end-member molecules are noninteractive; this observation is supported by others concerning molar volumes and vapor pressure relations, which indicate the presence of strong molecular-interaction forces that fundamentally affect the mixtures' physical properties. Since the rheological effects of partial crystallization parallel the characteristics of silicate lavas, icy satellite cryovolcanic morphologies are similarly interpretable with allowances for differences in surface gravities and lava densities.
The following must be assumed in order to derive the classic Burton-Prim-Slichter equation for segregation during crystal growth: isobaric, isothermal, isopotential or uncharged species, binary, planar interface, steady state, constant diffusion coefficient in fluid, no diffusion in crystal, no lateral convection within fluid film at interface with complete mixing beyond (stagnant film model), and either density, total concentration or partial molar volumes constant in the fluid phase. In addition, the effective distribution coefficient and the interfacial distribution coefficient must be defined properly. The velocity in the equation is the growth rate times a factor correcting for the difference in volumetric properties between crystal and fluid. The stagnant film thickness is found to be a function of freezing rate, with the precise functionality depending on the type of stirring occurring in the growth fluid.
The Intergovernmental Panel on Climate Change (IPCC) has reported that in the southeastern US and eastern China, the general greenhouse warming due to anthropogenic gaseous emissions is dominated by the cooling effect of anthropogenic aerosols. To verify this model prediction in eastern China and southeastern US, we analyzed regional patterns of climate changes at 72 stations in eastern China during 1951- 94 (44 years), and at 52 stations in the southeastern US during 1949-94 (46 years) to detect the fingerprint of aerosol radiative forcing. It was found that the mean rates of change of annual mean daily, maximum, minimum temperatures and diurnal temperature range (DTR) in eastern China were 0.8, -0.2, 1.8, and -2.0 C/100 years respectively, while the mean rates of change of annual mean daily, maximum, minimum temperatures and DTR in the southeastern US were -0.2, -0.6, 0.2, and -0.8 C/100 years, respectively. This indicates that the high rate of increase in annual mean minimum temperature in eastern China results in a slightly warming trend of daily temperature, while the high rate of decrease in annual mean maximum temperature and low rate of increase in annual mean minimum temperature lead to the cooling trend of daily temperature in the southeastern US. We found that the warming from the longwave forcing due to both greenhouse gases and aerosols was completely counteracted by the shortwave aerosol forcing in the southeastern US in the past 46 years. A slightly overall warming trend in eastern China is evident; winters have become milder. This finding is explained by hypothesizing that increasing energy usage during the past 44 years has resulted in more coal and biomass burning, thus increasing the emission of absorbing soot and organic aerosols in eastern China. Such emissions, in addition to well-known Asia dust and greenhouse gases, may be responsible for the winter warming trend in eastern China that we have reported here. The sensitivity of aerosol radiative properties to aerosol composition, size distribution, relative humidity (RH) is examined for the following aerosol systems: inorganic and organic ions (Cl-, Br-, NO3 -, SO4 2-, Na+, NH4 +, K+, Ca2+, Mg2+, HCOO-, CH3COO-, CH3CH2COO-, CH3COCOO-, OOCCOO2-, MSA-1); water-insoluble inorganic and organic compounds (elemental carbon, n-alkanes, SiO2, Al2O3, Fe2O3 and other organic compounds). The partial molar refraction method was used to calculate the real part of the refractive index. It was found that the asymmetry factor increased by approximately 48% with the real part varying from 1.40 to 1.65, and the single scattering albedo decreased by 24% with the imaginary part varying from -0.005 to -0.1. The asymmetry factor increased by 5.4 times with the geometric standard deviation varying from 1.2 to 3.0. The radiation transmission is very sensitive to the change in size distribution; other factors are not as significant. To determine the aerosol direct radiative forcing (ADRF), the aerosol optical depth (AOD) values at the three operational wavelengths (415, 500 and 673 nm) were determined at a regionally representative site, namely, Mt. Gibbs (35.78 deg N, 82.29 deg W, elevation 2006 m) in Mt. Mitchell State Park, NC, and a site located in an adjacent valley (Black Mountain, 35.66 deg N, 82.38 deg W, elevation 951 m) in the southeastern US. The two sites are separated horizontally by 10 km and vertically by 1 km. It was found that the representative total AOD values at 500 nm at the valley site for highly polluted (HP), marine (M) and continental (C) air masses were 0.68 +/- 0.33, 0.29 +/- 0.19 and 0.10 +/- 0.04, respectively. A search-graph method was used to retrieve the columnar size distribution (number concentration N, effective radius reff and geometric standard deviation=?g) from the optical depth observations at three operational wavelengths. The ground albedo, single scattering albedo and imaginary part of the refractive index were calculated using a mathematically unique procedure involving a Mie code and a radiative transfer code in conjunction with the retrieved aerosol size distribution, AOD, and diffuse-direct irradiance ratio. It was found that N, r(eff) and sigma(g) were in the ranges of 10 to 1.7 x 10(exp 4)/cubic cm, 0.09 to 0.68 micrometers and 1.12 to 2.95, respectively. The asymmetry factor and single scattering albedo were in the ranges of 0.63 to 0.75 and 0.74 to 0.97 respectively. The ground albedo for the forested terrain and imaginary part of refractive index were found to be in the ranges of 0.06 to 0.29 and 0.005 to 0.051 respectively. On the basis of these aerosol radiative properties obtained at the research sites and computations using the Column Radiation Model (CRM) of National Center of Atmospheric Research (NCAR) Community Climate Model (CCM3), it was found that the average cloud-free 24-hour ADRF values were -13 +/- 8, -8 +/- 3, -33 +/- 16 W/square m for marine, continental, and polluted air masses, respectively. On the assumption that the fractional coverage of clouds is 0.61, it was estimated that the annual mean ADRF was 7 +/- 2 W/square m in the southeastern US. The review with respect to the current knowledge of organic acids shows that aerosol formate and acetate concentrations range from 0.02 to 5.3 nmol/cubic m and from 0.03 to 12.4 nmol/cubic m respectively, and that between 34% to 77% of formate and between 21% to 66% of acetate are present in the fine fraction of aerosols. It was found that although most (98-99%) of these volatile organic acids were present in the gas phase, their concentrations in the aerosol particles were sufficient to make them a good candidate for cloud condensation nuclei (CCN). It is hypothesized that organic acids are at least one of the primary sources of CCN in the atmosphere due to their ubiquitous presence in the troposphere, especially over the continental forested areas. The results of our measurements at Palmer Station, Antarctica show that the daily average CCN concentrations at 0.3% and 1% supersaturations ranged from 0.3 to 160/cubic cm and from 4 to 168/cubic cm, respectively, during the period from 17 January to 26 February, 1994. New evidence for substantial and definitive CCN enhancement near and within cloud has been observed at Mt. Mitchell, North Carolina. The results show that the average monthly CCN concentrations were 460 +/- 217, 386 +/- 286, 429 +/- 228 and 238 +/- 134/cubic cm for in-cloud, overcast, clear and rainy conditions, respectively. The typical CCN spectra show that there were a lot of small CCN produced and the ion concentrations (especially H+ and SO4 2-) were very high during the CCN enhancement period. The significantly positive correlation between black carbon (BC) and CCN at 1% supersaturation indicates that a percentage of the BC measured at the site may be in the form of an internal mixture and participated in the formation of CCN.
The activity of carbon in the two-phase regions - W + WC and W + W2C was obtained from the carbon content of iron rods equilibrated with mixtures of metal plus carbide powders. From this activity data the standard free energies of formation of WC and W2C were calculated. The temperature of the invariant reaction W2C = W + WC was fixed at 1570 + or - 5K. Using available solubility data for C in solid W, the partial molar free energy of C in the dilute solid solution was also calculated. The heat of solution of C in W, and the excess entropy for the interstitial solid solution, were computed, assuming that the carbon atoms reside in the octahedral interstices of bcc W.
The partial pressures of Te2 in equilibrium with Ga(1-x)Te(x) samples were measured by optical absorption technique from 450 to 1100 C for compositions, x, between 0.333 and 0.612. To establish the relationship between the partial pressure of Te, and the measured optical absorbance, the calibration runs of a pure Te sample were also conducted to determine the Beer's Law constants. The partial pressures of Te2 in equilibrium with the GaTe(s) and Ga2Te3(s)compounds, or the so-called three-phase curves, were established. These partial pressure data imply the existence of the Ga3Te4(s) compound. From the partial pressures of Te2 over the Ga-Te melts, partial molar enthalpy and entropy of mixing for Te were derived and they agree reasonable well with the published data. The activities of Te in the Ga-Te melts were also derived from the measured partial pressures of Te2. These data agree well with most of the previous results. The possible reason for the high activity of Te measured for x less than 0.60 is discussed.