Possible precursors and products of deep hydrodesulfurization of gasoline and distillate fuels IV. Heat capacities,enthalpy increments,vapor pressures,and derived thermodynamic functions for dicyclohexylsulfide between the temperatures (5 and 520) K

Measurements leading to the calculation of the standard thermodynamic properties for gaseous dicyclohexylsulfide (Chemical Abstracts registry number [7133-46-2]) are reported. Experimental methods include adiabatic heat-capacity calorimetry, and inclined-piston gauge manometry combined with earlier reported measurements of combustion calorimetry, vibrating-tube densitometry, comparative ebulliometry, and differential-scanning calorimetry (d.s.c.). Critical properties are estimated for dicyclohexylsulfide. Standard molar entropies, standard molar enthalpies, and standard molar Gibbs free energies of formation are derived at selected temperatures between (298.15 and 520) K.     

Heat capacities and thermodynamic functions of hexagonal ice from T = 0.5 K to T = 38 K

The heat capacity of water in the form of hexagonal ice was measured between T = 0.5 K and T = 38 K using a semi-adiabatic calorimetric method. Since heat capacity data below T = 2 K have never been measured for water, this study presents the lowest measured values of the specific heat of water to date. Fits of the data were used to generate thermodynamic functions of water at smoothed temperatures between 0.5 K and 38 K. Both our experimental heat capacities and calculated enthalpy increments agree well with previously published values and thus supplement other studies well.     

Heat capacities and derived thermodynamic properties of lithium,sodium, and potassium disilicates from T = (5 to 350) K in both vitreous and crystalline states

Cryogenic heat capacities determined by equilibrium adiabatic calorimetry from T = (6 to 350) K on Li, Na, and K disilicates in both crystalline and vitreous phases are adjusted to end member composition and the vitreous/crystal difference ascertained. The thermophysical properties of these and related phases are estimated, compared, and updated. The values at T = 298.15 K of {S^∘(T) − S^∘(0)}/R for stoichiometric compositions of alkali disilicate (M₂O · 2SiO₂): vitreous, crystal: Li, 16.30, 14.65; Na, 20.67, 19.47; and K, 23.26, 23.00. Entropy differences confirm greater disorder in the vitreous compounds compared with the crystalline compounds. The entropy data also show that disorder increases with decreasing atomic mass of the alkali ion.     

Heat capacities of the mixtures of ionic liquids with methanol at temperatures from 283.15 K to 323.15 K

The molar isobaric heat capacities of (methanol + 1-hexyl-3-methylimidazolium tetrafluoroborate) and (methanol + 1-methyl-3-octylimidazolium tetrafluoroborate) mixtures have been determined over the temperature range from 283.15 K to 323.15 K within the whole composition range. The excess molar heat capacities of investigated mixtures have been fitted to the Redlich–Kister equation at several selected temperatures. Positive deviations from the additivity of molar heat capacities have been observed in both examined systems. The results obtained have been discussed in terms of molecular interactions in binary mixtures.     

Low-temperature heat capacities and derived thermodynamic functions of cyclohexane

The low-temperature heat capacities of cyclohexane were measured in the temperature range from 78 to 350 K by means of an automatic adiabatic calorimeter equipped with a new sample container adapted to measure heat capacities of liquids. The sample container was described in detail. The performance of this calorimetric apparatus was evaluated by heat capacity measurements on water. The deviations of experimental heat capacities from the corresponding smoothed values lie within ±0.3%, while the inaccuracy is within ±0.4%, compared with the reference data in the whole experimental temperature range. Two kinds of phase transitions were found at 186.065 and 279.684 K corresponding solid-solid and solid-liquid phase transitions, respectively. The entropy and enthalpy of the phase transition, as well as the thermodynamic functions {H_(T)-H _{298.15 K}} and {S _(T)-S_{298.15 K}}, were derived from the heat capacity data. The mass fraction purity of cyclohexane sample used in the present calorimetric study was determined to be 99.9965% by fraction melting approach. This revised version was published online in July 2006 with corrections to the Cover Date.     

Heat capacities and thermodynamic functions of d-ribose and d-mannose

The heat capacities of d-ribose and d-mannose have been studied over the temperature range from 1.9 to 440 K for the first time using a combination of Quantum Design Physical Property Measurement System and a differential scanning calorimeter. The purity, crystal phase and thermal stability of these two compounds have been characterized using HPLC, XRD and TG–DTA techniques, respectively. The heat capacities of d-Mannose have been found to be larger than those of d-ribose due to its larger molecular weight, and the solid–liquid transition due to the sample melting has also been detected in the heat capacity curve. The heat capacities of these two compounds have been fitted to a series of theoretical models and empirical equations in the entire experimental temperature region, and the corresponding thermodynamic functions have been derived based on the curve fitting in the temperature range from 0 to 440 K. Moreover, the phase transition enthalpy and melting temperature of these two compounds have also been determined from the heat flows obtained in DSC measurements.

     

Excess thermodynamic functions derived from densities and surface tensions of (p- or o-xylene + ethylene glycol dimethyl ether) between the temperatures (298.15 and 308.15) K

Densities (ρ) for binary systems of (p-xylene or o-xylene + ethylene glycol dimethyl ether) were measured over the full mole fraction range at the temperatures of (298.15, 303.15 and 308.15) K along with the densities of the pure components. The excess molar volumes (V^E) calculated from the density data show that the deviations from ideal behaviour in the two binary systems are negative, and they become more negative with the temperature increasing. Surface tensions (σ) of these binary systems were determined at the same temperatures (298.15, 303.15 and 308.15) K by the pendant drop method. The surface tension deviations (δσ) for p-xylene system are negative over the whole composition range, and become less negative with the temperature increasing, but for the o-xylene system, δσ are negative at high o-xylene concentration, and change to positive with the o-xylene concentration decreasing. The V^E and δσ were fitted to the Redlich–Kister polynomial equation. Surface tensions were also used to estimate surface entropy (S_σ) and surface enthalpy (H_σ).     

Densities and derived thermodynamic properties of 1-heptanol and 2-heptanol at temperatures from 313 K to 363 K and pressures up to 22 MPa

Experimental densities were determined in liquid phase for 1-heptanol and 2-heptanol at temperatures from 313 K to 363 K and pressures up to 22 MPa using a vibrating tube densimeter. Water and nitrogen were used as reference fluids for the calibration of the vibrating tube densimeter. The uncertainties of the experimental measurements in the whole range of reported data are estimated to be ±0.03 K for temperature, ±0.008 MPa for pressure, and ±0.20 kg · m^?3 for density. The experimental data are correlated using a short empirical equation of six parameters and the 11-parameter Benedict–Webb–Rubin–Starling equation of state (BWRS EoS) using a least square optimization. Statistical values to evaluate the different correlations are reported. Published density data of 1-heptanol are compared with values calculated with the 6-parameter equation using the parameters obtained in this work. The experimental data determined here are also compared with an available correlation for 1-heptanol. Densities of 2-heptanol at high pressure were not found in the literature and the data reported here represent the first set of data reported in the literature. Isothermal compressibilities and isobaric thermal expansivity are calculated using the 6-parameter equation for both alcohols within uncertainties estimated to be ±0.025 Gpa^?1 and ±4 × 10^?7 K^?1, respectively.     

Heat capacity and thermodynamic properties of germanium disulfide at temperatures from T = (2 to 1240) K

The heat capacity of polycrystalline germanium disulfide α-GeS₂ has been measured by relaxation calorimetry, adiabatic calorimetry, DSC and heat flux calorimetry from T = (2 to 1240) K. Values of the molar heat capacity, standard molar entropy and standard molar enthalpy are 66.191 J · K^?1 · mol^?1, 87.935 J · K^?1 · mol^?1 and 12.642 kJ · mol^?1. The temperature of fusion and its enthalpy change are 1116 K and 23 kJ · mol^?1, respectively. The thermodynamic functions of α-GeS₂ were calculated over the range (0 ? T/K ? 1250).     

Heat capacities and related thermal properties of DyNi5, HoNi5 and ErNi5 between 5 and 300 K

Heat capacity data and calculated thermodynamic functions are presented for DyNi₅, HoNi₅ and ErNi₅. λ-type thermal anomalies are noted at 12.0 K (DyNi₅), 4.1 K (HoNi₅) and 8.0 K (ErNi₅). Schottky-type anomalies are observed at higher temperatures. The λ and Schottky anomalies are ascribed to the destruction of ferromagnetic order and to crystal field excitation, respectively. A deficiency of magnetic entropy, compared to Rln(2J + 1), is noted corresponding roughly to Rln2. This suggests that the ground state in the ordered materials is a doublet. ErNi₅ is analyzed using a Hamiltonian containing terms representing the crystal field and magnetic interactions. The analysis shows that a doublet ground state can result with reasonable values of the crystal field parameters. The parameters are shown to be consistent with the heat capacity behavior of ErNi₅. Ordering temperatures are not proportional to the de Gennes function.     

Heat capacities and thermodynamic functions of the tellurates(IV) of zinc and cadmium

The temperature dependencies of the molar heat capacities of ZnTeO₃, Zn₂Te₃O₈, CdTeO₃ and CdTe₂O₅ are determined. The experimental data are statistically processed using the least squares method to determine the parameters in the equations for the corresponding compounds: C_p,m=a+b(T/K)-c(T/K)^-2. These equations and the standard molar entropies are used to determine Δ^T₀S⁰_m, Δ^T_TH⁰_m and (Φ⁰_m+Δ^T,₀H⁰_m/T) for T'=298.15 K.     

(p, ρ, T) Properties for n-butane in the temperature range from 280 K to 380 K at pressures up to 200 MPa

The (p, ρ, T) properties for n-butane in the compressed liquid phase were measured by means of a metal-bellows variable volumometer in the temperature range from 280 K to 380 K at pressures up to 200 MPa. The mole fraction purity of the n-butane used in the measurements was 0.9997. The expanded uncertainties (k = 2) in temperature, pressure, and density measurements have been estimated to be less than ±3 mK; 1.4 kPa (p ⩽ 7 MPa), 0.06% (7 MPa < p ⩽ 50 MPa), 0.1% (50 MPa < p ⩽ 150 MPa), and 0.2% (p > 150 MPa); and 0.09%, respectively. In the region above100 MPa at T = 280 K and T = 440 K, the uncertainty in density measurements increases from 0.09% to 0.13% and 0.22%, respectively. Eight (p, ρ, T) measurements at the same temperatures and pressures as the literature values have been conducted for comparisons. In addition, comparisons of the available equations of state with the present measurements are reported.     

Apparent molar volumes and apparent molar heat capacities of aqueous KI,HIO3, NaIO3, and KIO3 at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa

We determined apparent molar volumes V_? at 298.15 ? (T/K) ? 368.15 and apparent molar heat capacities C_p,? at 298.15 ? (T/K) ? 393.15 for aqueous solutions of HIO₃ at molalities m from (0.015 to 1.0) mol · kg^?1, and of aqueous KIO₃ at molalities m from (0.01 to 0.2) mol · kg^?1 at p = 0.35 MPa. We also determined V_? at the same p and at 298.15 ? (T/K) ? 368.15 for aqueous solutions of KI at m from (0.015 to 7.5) mol · kg^?1. We determined C_p,? at the same p and at 298.15 ? (T/K) ? 393.15 for aqueous solutions of KI at m from (0.015 to 5.5) mol · kg^?1, and for aqueous solutions of NaIO₃ at m from (0.02 to 0.15) mol · kg^?1. Values of V_? were determined from densities measured with a vibrating-tube densimeter, and values of C_p,? were determined with a twin fixed-cell, differential temperature-scanning calorimeter. Empirical functions of m and T were fitted to our results for each compound. Values of K_a, Δ_rH_m, and Δ_rC_p,m for the proton ionization reaction of aqueous HIO₃ are calculated and discussed.     

Apparent molar volumes and apparent molar heat capacities of aqueous tetrahydrofuran,dimethyl sulfoxide, 1,4-dioxane,and 1,2-dimethoxyethane at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa

We determined apparent molar volumes V_? at 278.15 ? (T/K) ? 368.15 and apparent molar heat capacities C_p,? at 278.15 ? (T/K) ? 393.15 at p = 0.35 MPa for aqueous solutions of tetrahydrofuran at m from (0.016 to 2.5) mol · kg^?1, dimethyl sulfoxide at m from (0.02 to 3.0) mol · kg^?1, 1,4-dioxane at m from (0.015 to 2.0) mol · kg^?1, and 1,2-dimethoxyethane at m from (0.01 to 2.0) mol · kg^?1. Values of V_? were determined from densities measured with a vibrating-tube densimeter, and values of C_p,? were determined with a twin fixed-cell, differential, temperature-scanning calorimeter. Empirical functions of m and T for each compound were fitted to our V_? and C_p,? results.     

Apparent molar volumes and apparent molar heat capacities of aqueous magnesium nitrate,strontium nitrate,and manganese nitrate at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa

Apparent molar volumes V_ϕ and apparent molar heat capacities C_p,ϕ were determined at the pressure 0.35 MPa for aqueous solutions of magnesium nitrate Mg(NO₃)₂ at molalities m = (0.02 to 1.0) mol · kg⁻¹, strontium nitrate Sr(NO₃)₂ at m = (0.05 to 3.0) mol · kg⁻¹, and manganese nitrate Mn(NO₃)₂ at m = (0.01 to 0.5) mol · kg⁻¹. Our V_ϕ values were calculated from solution densities obtained at T = (278.15 to 368.15) K using a vibrating-tube densimeter, and our C_p,ϕ values were calculated from solution heat capacities obtained at T = (278.15 to 393.15) K using a twin fixed-cell, differential, temperature-scanning calorimeter. Empirical functions of m and T were fitted to our results, and standard state partial molar volumes and heat capacities were obtained over the ranges of T investigated.     

Excess thermodynamic properties of binary mixtures of N,N-dimethylacetamide with water or water-d2 at temperatures from 277.13 K to 318.15 K

Densities of binary mixtures of N,N-dimethylacetamide (DMA) with water (H₂O) or water-d₂ (D₂O) were measured at the temperatures from T=277.13 K to T=318.15 K by means of a vibrating-tube densimeter. The excess molar volumes V_m^E, calculated from the density data, are negative for the (H₂O + DMA) and (D₂O + DMA) mixtures over the entire range of composition and temperature. The V_m^E curves exhibit a minimum at x(DMA)≅0.4. At each temperature, this minimum is slightly deeper for the (D₂O + DMA) mixtures than for the corresponding (H₂O + DMA) mixtures. The difference between D₂O and H₂O systems becomes smaller when the temperature increases. The V_m^E results were correlated using a modified Redlich–Kister expansion. The partial molar volume of DMA plotted against x(DMA) goes through a sharp minimum in the water-rich region around x(DMA)≅0.08. This minimum is more pronounced the lower the temperature and is deeper in D₂O than in H₂O at each temperature. Again, the difference becomes smaller as the temperature increases. The excess expansion factor α^E plotted against x(DMA) exhibit a maximum in the water rich region of the mole fraction scale. At each temperature, this maximum is higher for the (D₂O + DMA) mixtures than for the corresponding (H₂O + DMA) mixtures, and the difference becomes smaller as the temperature increases. At its maximum, α^E can be even more than 25 per cent of total value of the cubic expansion coefficient α in the (H₂O + DMA) and (D₂O + DMA) mixtures.