USGS Science⌕ Search

SEARCH · USGS Science

Results for “Journal of Chemical Thermodynamics”

Search indexed USGS publications on groundwater, aquifers, geologic maps, mineral resources and earthquakes. Explore source records by subject and place.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 recordsLinked to original sources
USGS1985

Low-temperature heat capacity and entropy of chalcopyrite (CuFeS2): estimates of the standard molar enthalpy and Gibbs free energy of formation of chalcopyrite and bornite (Cu5FeS4)

The heat capacity of CuFeS2 (chalcopyrite) was measured between 6.3 and 303.5 K. At 298.15 K, Cp,mo and Smo(T) are (95.67??0.14) J??K-1??mol-1 and (124.9??0.2) J??K-1??mol-1, respectively. From a consideration of the results of two sets of equilibrium measurements we conclude that ??fHmo(CuFeS2, cr, 298.15 K) = -(193.6??1.6) kJ??mol-1 and that the recent bomb-calorimetric determination by Johnson and Steele (J. Chem. Thermodynamics 1981, 13, 991) is in error. The standard molar Gibbs free energy of formation of bornite (Cu5FeS4) is -(444.9??2.1) kJ??mol-1 at 748 K. ?? 1985.

Journal of Chemical Thermodynamics↗
USGS1976

Thermodynamics of Fe(II)Fe(III) oxide systems I. Hydrothermal Fe3O4

The heat capacity of a hydrothermally-prepared polycrystalline sample of Fe3O4 was measured from 53 to 350 K, primarily to study the thermophysics of the Verwey transitions. Although the bifurcation of the transition was confirmed, the sample was found to contain traces of manganese. The observed transition temperatures of 117.0 and 123.0 K are 3.7 and 4.2 K higher respectively than those found in pure Fe3O4. Ancillary analytical results are consistent and indicate a stoichiometry of Mn0.008Fe2.992O4 for this material. Characteristics in the transition region are ascribed to dopant effects. ?? 1976.

Journal of Chemical Thermodynamics↗
USGS1996

Thermodynamic properties of scapolites at temperatures ranging from 10 K to 1000 K

The heat capacities of five mineral samples from the scapolite solid-solution series, Na4Al3Si9O24Cl (marialite) to Ca4Al6Si6O24CO3 (meionite), were measured by the adiabatic method from T=8 K to T=350 K and by the differential scanning calorimetry (d.s.c.) method from T = 300 K to T = 1000 K. The meionite (Me) content in per cent {Me=100 Ca*/(Ca* + Na*)} (where the asterisk indicates that possible substituents are included) and molar heat capacity (Cp,m/R) at T=298.15 K for each sample is: Me28, 82.07; Me44, 82.09; Me55, 83.95; Me69, 85.80; Me88, 84.54. The standard molar entropies, {S,om(298.15 K)-Som(0 K)} R-1 (R=8.31451 J??K-1??mol-1), at T=298.15 K for the respective compositions are: 85.05??0.26, 83.78??0.50, 85.22??0.24, 85.76??0.21, and 84.17??0.59. The calculated standard molar entropies (as above) at T=298.15 K for the end-members marialite and meionite, and for an intermediate composition (mizzonite=Me75) are 84.85, 83.94 and 86.15, respectively. Values of the coefficients in the equation Cp,m/R = a + bT+ cT2 + dT-1/2 + eT-2 (valid from T = 300 K to T =1000 K) are: (Mex, a, b/K, c/K2, d/K-1/2, e/K-2 Me88), 315.580, -0.0795676, 1.52825.10-5, -3954.83, 1808460; Me69, 261.285, -0.0415017, 8.73053.10-7, -3028.28, 1083666; Me55, 232.236, -0.0352222, 6.49875.10-6, 2505.99, 601750; Me44, 276.696, -0.0756614, 2.39722.10-5, -3210.40, 1044363; Me28, 149.917, 0.0229399, -1.23180.10-5, 1208.87, -318470. Smoothed thermodynamic functions for the five samples are also presented. The enthalpies of solution for five natural scapolites were measured in 2PbO??B2O3 melts at T= 973 K by Calvet-type calorimetry. The values of ??solHom/R??K are: Me11, 32.14??0.7; Me28, 32.34??0.4; Me44, 33.66??0.8; Me69, 35.29??0.8; Me88, 32.87??0.3. The calculated enthalpies of formation for stoichiometric scapolites ??fHom/103??R??K at T= 298.15 K are: Me0, -1467.4??1.3; Me11, -1491.2??1.2; Me28, -1527.6??0.9; Me44, -1564.1??1.1; Me55, -1587.4??1.1; Me69, -1619.7??1.1; Me75, -1633.1??1.1; Me88, -1649.1??1.0; Me100, -1664??1.6. The heat capacity, the entropy, and the enthalpy of solution have maximal values near Me75 which may account in part for the relatively common occurrence of that composition in natural assemblages. Earlier measurements on leucite have been extended by the Komada/Westrum phonon dispersion model and corrected to end-member composition. ?? 1996 Academic Press Limited.

Journal of Chemical Thermodynamics↗
USGS1985

Low-temperature molar heat capacities and entropies of MnO2 (pyrolusite), Mn3O4 (hausmanite), and Mn2O3 (bixbyite)

Pyrolusite (MnO2), hausmanite (Mn3O4), and bixbyite (Mn2O3), are important ore minerals of manganese and accurate values for their thermodynamic properties are desirable to understand better the {p(O2), T} conditions of their formation. To provide accurate values for the entropies of these important manganese minerals, we have measured their heat capacities between approximately 5 and 380 K using a fully automatic adiabatically-shielded calorimeter. All three minerals are paramagnetic above 100 K and become antiferromagnetic or ferrimagnetic at lower temperatures. This transition is expressed by a sharp ??-type anomaly in Cpmo for each compound with Ne??el temperatures TN of (92.2??0.2), (43.1??0.2), and (79.45??0.05) K for MnO2, Mn3O4, and Mn2O3, respectively. In addition, at T ??? 308 K, Mn2O3 undergoes a crystallographic transition, from orthorhombic (at low temperatures) to cubic. A significant thermal effect is associated with this change. Hausmanite is ferrimagnetic below TN and in addition to the normal ??-shape of the heat-capacity maxima in MnO2 and Mn2O3, it has a second rounded maximum at 40.5 K. The origin of this subsidiary bump in the heat capacity is unknown but may be related to a similar "anomalous bump" in the curve of magnetization against temperature at about 39 K observed by Dwight and Menyuk.(1) At 298.15 K the standard molar entropies of MnO2, Mn3O4, and Mn2O3, are (52.75??0.07), (164.1??0.2), and (113.7??0.2) J??K-1??mol-1, respectively. Our value for Mn3O4 is greater than that adopted in the National Bureau of Standards tables(2) by 14 per cent. ?? 1985.

Journal of Chemical Thermodynamics↗
USGS1997

Molar heat capacity and entropy of calcium metal

The heat capacity of calcium has been measured at 85 mean temperatures between T ≈ 8 K and T ≈ 369 K using an adiabatically-shielded calorimeter in an intermittent heating mode. At T = 298.15 K, the recommended values for the molar heat capacity, molar entropy, and molar enthalpy increment referred to T = 0 are (25.77 ± 0.08) J·K −1 ·mol −1 , (42.90 ± 0.11) J·K −1 ·mol −1 , and (5811 ±12)J·mol −1 , respectively. The uncertainties are twice the standard deviation of the mean.

Journal of Chemical Thermodynamics↗
USGS1989

Heat capacities and entropies at 298.15 K of MgTiO3 (geikielite), ZnO (zincite), and ZnCO3 (smithsonite)

Heat capacities of synthetic MgTiO3 (geikielite), ZnO (zincite), and natural crystals of smithsonite (ZnCO3) were measured between 9 and 366 K using an automatic adiabatically shielded calorimeter. At 298.15 K the standard molar entropies Smo of MgTiO3, ZnO, and ZnCO3 are (74.64 ?? 0.15), (43.16 ?? 0.09), and (81.19 ?? 0.16) J??K-1??mol-1, respectively. Debye temperatures for MgTiO3 and ZnO calculated from our Cp, mo values below 20 K are (900 ?? 20) K and (440 ?? 25) K respectively. Heat capacities for MgTiO3 and ZnO were combined with enthalpy increments from the literature to derive heat-capacity equations for these phases from 260 to about 1800 K. The heat capacities of MgTiO3 between 260 and 1720 K were fitted with an average deviation of 0.3 per cent by the equation: C??p,m/(J??K-1??mol-1) = 222.5-0.05274(T/K)-6.092x105(T/K)-1-1874.6(T/K) -1/2+1.878x10-5(T/K)2 and for ZnO the equation: C??p,m/(J??K-1??mol-1) = 53.999+7.851x10-4(T/K)-5.868x105(T/K)-2 -127.50(T/K)-:1/2+1.9376x10-6(T/K)2 fits the heat capacities in the temperature interval of 250 to 1800 K with an average deviation of 0.7 per cent. ?? 1989.

Journal of Chemical Thermodynamics↗
USGS2007

Geochemical interpretations of groundwater flow systems

Interest in the geochemistry of groundwater is increasing owing to the great number of current projects involving underground liquid waste storage, artificial recharge of potable water, accidental contamination of groundwater bodies, sanitary landfills, and pollution monitoring. Geochemical techniques used to facilitate the understanding of a groundwater system range from extremely simple to those requiring sophisticated theories, equipment, and procedures. An interpretation of the simple trilinear diagram for samples collected from the Yucatan Peninsula of Mexico provided evidence that the fresh-water body was only a few tens of meters thick and was underlain everywhere by an extensive body of salt water. A geochemical technique that has been used effectively to identify the source of salt water in coastal aquifers is measurement of the carbon-14 concentrations. Carbon-14 has been used in a regional carbonate aquifer to determine the velocity of groundwater movement, rates of chemical reactions, and distribution of hydraulic conductivity. The application of principles of irreversible thermodynamics to groundwater systems provides a basis for constructing models which permit prediction, over both time and space, of changes in head distribution and chemical character of the water resulting from imposed stresses on the system. In essence, proper application of irreversible thermodynamics combines the potential theory of Hubbert with principles of reversible chemical thermodynamics, such as solution of carbonate minerals, to describe and explain controlling chemical reactions and processes of groundwater systems.

Florida, South Carolina↗
USGS1973

Chemical composition of a saline lake on Enderbury Island, Phoenix Island Group, Pacific Ocean

Ion activity products for the dissolution of calcite, aragonite, gypsum, monetite, brushite, dolomite, magnesite, hydroxyapatite, and fluorapatite were calculated for a South Pacific guano island brine with an ionic strength of 6.4. Environmental conditions for the brine at the time of analysis and of sampling indicated saturation with respect to calcite, aragonite, gypsum, hydroxyapatite and fluorapatite; a comparison of the ion activity products and equilibrium constants indicated saturation or supersaturation with respect to most minerals found in lake sediments or elsewhere on the island. The results suggest that chemical thermodynamic calculations for brines may have some usefulness despite the many assumptions and estimations that must be made.

Journal of Research of the U.S. Geological Survey↗
USGS2005

Geochemistry and the understanding of ground-water systems

Geochemistry has contributed significantly to the understanding of ground-water systems over the last 50 years. Historic advances include development of the hydrochemical facies concept, application of equilibrium theory, investigation of redox processes, and radiocarbon dating. Other hydrochemical concepts, tools, and techniques have helped elucidate mechanisms of flow and transport in ground-water systems, and have helped unlock an archive of paleoenvironmental information. Hydrochemical and isotopic information can be used to interpret the origin and mode of ground-water recharge, refine estimates of time scales of recharge and ground-water flow, decipher reactive processes, provide paleohydrological information, and calibrate ground-water flow models. Progress needs to be made in obtaining representative samples. Improvements are needed in the interpretation of the information obtained, and in the construction and interpretation of numerical models utilizing hydrochemical data. The best approach will ensure an optimized iterative process between field data collection and analysis, interpretation, and the application of forward, inverse, and statistical modeling tools. Advances are anticipated from microbiological investigations, the characterization of natural organics, isotopic fingerprinting, applications of dissolved gas measurements, and the fields of reaction kinetics and coupled processes. A thermodynamic perspective is offered that could facilitate the comparison and understanding of the multiple physical, chemical, and biological processes affecting ground-water systems.

Hydrogeology Journal↗
USGS1998

Critical evaluation and selection of standard state thermodynamic properties for chromium metal and its aqueous ions, hydrolysis species, oxides, and hydroxides

This review critically evaluates the reported thermodynamic data on chromium metal, oxides, hydroxides, free aqueous ions, and hydrolysis species. Several discrepancies and inconsistencies have been uncovered and resolved to improve equilibrium calculations for chemical modeling and related engineering purposes. A revised set of data is derived from evaluation of electrochemical measurements, silver chromate solubility measurements, and auxiliary post-1980 data, reevaluation of earlier data, and reconsideration of the path for the thermodynamic network. The recommended thermodynamic values for Cr (cr) , C , C , Cr , Cr 2 , Cr 2 O 3(cr) , CrO 3(cr) , FeCr 2 O 4(cr) , CrCl 2(cr) , CrCl 3(cr) , and KFe 3 (CrO 4 ) 2 (OH) 6(cr) at 25 °C, 1 bar, and infinite dilution are given.

Journal of Chemical & Engineering Data↗
USGS2016

Groundwater

Introduction Groundwater represents the terrestrial subsurface component of the hydrologic cycle. As such, groundwater is generally in motion, moving from elevated areas of recharge to lower areas of discharge. Groundwater usually moves in accordance with Darcy’s law (Dalmont, Paris: Les Fontaines Publiques de la Ville de Dijon, 1856). Groundwater residence times can be under a day in small upland catchments to over a million years in subcontinental-sized desert basins. The broadest definition of groundwater includes water in the unsaturated zone, considered briefly here. Water chemically bound to minerals, as in gypsum (CaSO 4 • 2H 2 O) or hydrated clays, cannot flow in response to gradients in total hydraulic head (pressure head plus elevation head); such water is thus usually excluded from consideration as groundwater. In 1940, M. King Hubbert showed Darcy’s law to be a special case of thermodynamically based potential field equations governing fluid motion, thereby establishing groundwater hydraulics as a rigorous engineering science ( Journal of Geology 48, pp. 785–944). The development of computer-enabled numerical methods for solving the field equations with real-world approximating geometries and boundary conditions in the mid-1960s ushered in the era of digital groundwater modeling. An estimated 30 percent of global fresh water is groundwater, compared to 0.3 percent that is surface water, 0.04 percent atmospheric water, and 70 percent that exists as ice, including permafrost ( Shiklomanov and Rodda 2004 , cited under Groundwater Occurrence ). Groundwater thus constitutes the vast majority—over 98 percent—of the unfrozen fresh-water resources of the planet, excluding surface-water reservoirs. Environmental dimensions of groundwater are equally large, receiving attention on multiple disciplinary fronts. Riparian, streambed, and spring-pool habitats can be sensitively dependent on the amount and quality of groundwater inputs that modulate temperature and solutes, including nutrients and dissolved oxygen. Groundwater withdrawals can negatively impact riparian habitats by depriving ecosystems of adequate fresh water and fragmenting communities when streams go dry. Biochemical reactions in shallow groundwater can remove anthropogenically elevated nitrogen compounds and reduce—but only to a point—the greening of waterways and shorelines with periphyton and harmful algal blooms. Groundwater extraction for beneficial use is increasingly limited by water-quality constraints imposed by naturally occurring and introduced substances. Overdrafting can cause land-surface subsidence, damaging buildings and roads and disrupting canals, sewers, and other gravity-flow conveyances. Increases in groundwater levels can cause soil salinization in dry regions and erosive sapping and flooding in wet regions. Coastal saltwater intrusion, groundwater flooding, salinization associated with groundwater-irrigated agriculture, induced seismicity from injected wastes, and the detrimental impacts of groundwater depletion are among the major environmental challenges of our time.

Book chapter↗
USGS1974

WATEQ, a computer program for calculating chemical equilibria of natural waters

The computer program, WATEQ, calculates the equilibrium distribution of inorganic aqueous species of major and important minor elements in natural waters using the chemical analysis and in situ measurements of temperature, pH, and redox potential. From this model, the states of reaction of the water with solid and gaseous phases are calculated. Thermodynamic stabilities of aqueous species, minerals, and gases have been selected from a careful consideration of all available experimental data. The program is written in PL-1 for IBM 360 computers.

Journal of Research of the U.S. Geological Survey↗
USGS2012

American hydrogeology at the millennium: An annotated chronology of 100 most influential papers

Hydrogeology developed as scientists undertook activities to describe how a groundwater system functions to explain why it is that way, in order to solve practical problems of water supply. This paper demonstrates the evolutionary nature and growth of hydrogeology in the United States on the basis of a selection of one hundred papers that had a significant impact on subsequent activities. We have identified three revolutionary concepts that resulted directly from this evolutionary understanding and have selected papers that demonstrate important consequences. These three concepts are 1) that the mathematical expression for heat flow can be paraphrased for groundwater and used in transient flow conditions to determine aquifer characteristics; 2) that the distribution of fluid potential can be formulated in mathematical equations suitable for solution by various analytical techniques; and 3) that chemical thermodynamics can be applied to hydrogeologic systems in order to understand the processes controlling the chemical character of groundwater. One purpose of this paper is to encourage scientists to gain an additional dimension of satisfaction from their work by being aware of the contributions of those who went before them and to see how their own work fits into the current understanding of hydrogeology.

Hydrogeology Journal↗
USGS2020

Timescales and processes of methane hydrate formation and breakdown, with application to geologic systems

Gas hydrate is an ice-like form of water and low molecular weight gas stable at temperatures of roughly -10ºC to 25ºC and pressures of ~3 to 30 MPa in geologic systems. Natural gas hydrates sequester an estimated one-sixth of Earth’s methane and are found primarily in deepwater marine sediments on continental margins, but also in permafrost areas and under continental ice sheets. When gas hydrate is removed from its stability field, its breakdown has implications for the global carbon cycle, ocean chemistry, marine geohazards, and interactions between the geosphere and the ocean-atmosphere system. Gas hydrate breakdown can also be artificially driven as a component of studies assessing the resource potential of these deposits. Furthermore, geologic processes and perturbations to the ocean-atmosphere system (e.g., warming temperatures) can cause not only dissociation, but also more widespread dissolution of hydrate or even formation of new hydrate in reservoirs. Linkages between gas hydrate and disparate aspects of Earth’s near-surface physical, chemical, and biological systems render an assessment of the rates and processes affecting the persistence of gas hydrate an appropriate Centennial Grand Challenge. This paper reviews the thermodynamic controls on methane hydrate stability and then describes the relative importance of kinetic, mass transfer, and heat transfer processes in the formation and breakdown (dissociation and dissolution) of gas hydrate. Results from numerical modeling, laboratory, and some fields studies are used to summarize the rates of hydrate formation and breakdown, followed by an extensive treatment of hydrate dynamics in marine and cryospheric gas hydrate systems.

Journal of Geophysical Research-Solid Earth↗
USGS2006

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

Journal of Physical Chemistry B↗
USGS2019

Prediction of ice‐free conditions for a perennially ice‐covered Antarctic lake

Although perennially ice‐covered Antarctic lakes have experienced variable ice thicknesses over the past several decades, future ice thickness trends and associated aquatic biological responses under projected global warming remain unknown. Heat stored in the water column in chemically stratified Antarctic lakes that have middepth temperature maxima can significantly influence the ice thickness trends via upward heat flux to the ice/water interface. We modeled the ice thickness of the west lobe of Lake Bonney, Antarctica, based on possible future climate scenarios utilizing a 1D thermodynamic model that accounts for surface radiative fluxes as well as the heat flux associated with the temperature evolution of the water column. Model results predict that the ice cover of Lake Bonney will shift from perennial to seasonal within one to four decades, a change that will drastically influence ecosystem processes within the lake.

Journal of Geophysical Research F: Earth Surface↗
USGS1995

Entropy of adsorption of mixed surfactants from solutions onto the air/water interface

The partial molar entropy change for mixed surfactant molecules adsorbed from solution at the air/water interface has been investigated by surface thermodynamics based upon the experimental surface tension isotherms at various temperatures. Results for different surfactant mixtures of sodium dodecyl sulfate and sodium tetradecyl sulfate, decylpyridinium chloride and sodium alkylsulfonates have shown that the partial molar entropy changes for adsorption of the mixed surfactants were generally negative and decreased with increasing adsorption to a minimum near the maximum adsorption and then increased abruptly. The entropy decrease can be explained by the adsorption-orientation of surfactant molecules in the adsorbed monolayer and the abrupt entropy increase at the maximum adsorption is possible due to the strong repulsion between the adsorbed molecules.

Journal of the Chemical Society, Faraday Transacti↗