Second virial coefficients of polar gases for a four-parameter model

The second virial coefficients of polar gases have been studied for a potential function consisting of the Kihara spherical core potential combined with a preaveraged dipole-dipole interaction term. The molecular parameters ?/κ, ρ_o, a*, and y of this potential function were determined for ten substances by a nonlinear least squares analysis of experimental second virial coefficients. These molecular parameters were related to the critical constants, acentric factors, and fourth parameters of the substances. The resulting equations reproduced the second virial coefficients to within the accuracy of the data. Comparisons with experimental data for substances not included in the development of the relationships indicated that good agreement can be obtained for polar fluids by the method of this study.     

Mixing rules for predicting the viscosity of bitumens saturated with pure gases

Mixing rules are developed and evaluated for predicting the viscosity of Alberta bitumens saturated with each of N₂, CO, CH₄, CO₂ and C₂, H₆. The viscosity-temperature variation for all bitumens and gases is expressed as [log(μ + 0.8) = ± 10 T]. A linear cross-correlation between parameters b₁ and b₂ in the above relationship is identified and used subsequently to derive a one-parameter viscosity equation: [log(μ + 0.8) = θ(ΦT)^b]. where θ = 160, Φ = 0.008 for all bitumens and θ = -0.1, Φ = 0.015 for all gases. The two mixing rules examined in this study are: $ \log \left( {\bar \mu + 0.8} \right) = \sum v_i \,\log \left( {\mu _i + 0.8} \right) $ and $ \log \left( {\bar \mu + 0.8} \right) = \sum v_i \,\log \left( {\mu _i + 0.8} \right) + \sum \sum v_i v_j B_{ij} $, where v represents the geometric mean of mass and mole fractions and B_ij is a binary viscous interaction term. Predictions for the viscosity of gas-saturated bitumens are validated with over 400 experimental data points for five Alberta bitumens at temperatures from 12 to 120°C and pressures up to 10 MPa.     

Comparison of various solvents for determination of intrinsic viscosity and viscometric constants for cellulose

Different solvents used to determine the intrinsic viscosity and the viscometic constants, a and K, published in the literature for cellulose, were compared. The various parameters affecting the viscometric constants were also evaluated. The main conclusions obtained from the experimental data available in the literature are that (1) the intrinsic viscosities in various solvents are ordered as follows: [η]_LiCl/DMAc > [η]_NH3/NH4SCN ≥ [η]_FeTNa > [η]_CED > [η]_Cadoxen > [η]_Cuoxam; (2) the reported intrinsic viscosities and molecular weights for cellulose are lower than the true value due to degradation of cellulose in the solvents; (3) the rate of degradation was the smallest in LiCl/DMAc and NH₃/NH₄SCN, moderate in cadoexn and FeTNa, and the highest in CED and cuoxam; (4) the plot of log K versus exponent a was linear and inversely related; (5) the curve was used for estimation of the constant K for cellulose in a solvent (NH3/NH4SCN) with a known exponent a; and (6) among various reported solvents, LiCl/DMAc and NH₃/NH₄SCN are advantageous over other solvents because of a complete dissolution of the polymer with a negligible reduction in its intrinsic viscosity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2189–2193, 2002     

Interchain force field and elastic constants of polytetrafluoroethylene

Neutron inelastic scattering spectroscopy has been used to determine the phonon dispersion curve for longitudinal lattice vibrations perpendicular to the chain axes in hexagonal polytetrafluoroethylene at 25°C. By the nature of the method measurements are confined to the microcrystalline regions of the polymer and in addition to providing information about the intermolecular force field it is possible to calculate the crystalline elastic constant, C₁₁, perpendicular to the chains as 18.2 + 0.2×10¹⁰ dyne cm⁻².     

Measurement of the gradient of viscosity with composition of mixtures of non-ideal gases

A perturbation viscometer is a differential capillary viscometer that measures the logarithmic viscosity gradient of the viscosity-composition curve for gas mixtures. Measurements are made at different gas mixture compositions. Integration of the logarithmic viscosity gradients measured over the full composition range gives the mixture viscosity relative to the viscosity of one of the pure components of the gas mixture. This method is attractive because, for measurements of equal precision, integration of the gradients is potentially an order of magnitude more precise than measurement of the viscosities directly. It can also work at high and low temperatures and perhaps high pressures.The perturbation viscometer has been used to make measurements on ideal gas mixtures at ambient and elevated temperatures. The situation is more complicated when the gas mixtures are non-ideal. Extra effects due to density differences, molar volume change on mixing and differential thermal expansion may be measured in addition to the desired viscosity change producing systematic errors in the results. Thus, a more sophisticated apparatus is required. The standard perturbation viscometer has been modified to separate out the extra effects to permit measurement of the true change in viscosity. In addition, the theoretical operation of the modified apparatus has been revised to account for the design changes to permit calculation of the viscosity-composition profiles from the results.The apparatus has been tested using helium-HFC-125 mixtures and two new viscosity-composition profiles are presented for these mixtures at 23 and . Internal consistency tests have been used to confirm that the data produced are of high quality with an estimated uncertainty in the viscosity ratio data at of 0.9% and at of 1.5%.     

Applicability of the redlich-kwong equation of state and its modifications to polar gases

The constants of the Redlich-Kwong equation of state were optimized for each available isotherm using the experimental P-v-T data of nonpolar, slightly     

On predicting self-diffusion coefficients from viscosity in gases and liquids

The relations between self-diffusion and viscosity for compressed liquids and gases have been reviewed, and a new equation for correlating viscosities over wide ranges of temperature and pressure is proposed. This formula is inspired by the Lennard-Jones Chain model of Yu and Gao for self-diffusion, and represents the viscosities of 15 compounds (1046 data points) with an average absolute deviation of 6.95%. Moreover, as the presented equation and the Yu-Gao model require the same fitting parameters, the ability to calculate self-diffusion coefficients from the viscosity parameter is studied. Some of the classic reviewed relations, such as the Stokes-Einstein formula, are also contrasted with the available experimental data of both transport properties.     

A new analytical method to calculate intrinsic viscosity and viscosity constants of polymer–solvent systems

Experimental viscosities were measured by Schott Gerate viscometer at 30 °C for polystyrene–chloroform and polycaprolactum–benzene systems. These data were analyzed by a newly developed analytical method to calculate intrinsic viscosity and viscosity constants. The analytical method was compared with the graphical as well as the least squares methods and the new analytical method is better than the graphical method because it avoids personal errors that might arise in reading the intercept and slope values from the reduced viscosity versus concentration plots. Furthermore, the analytical method is as effective as the least squares method, but provides better insights while choosing the experimental viscosity values. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 283–290, 2002     

High pressure fugacity coefficients from equilibria of simple gases and polar liquids

An equation of state for mixtures proposed by De Santis, Breedveld and Prausnitz was used to predict the fugacity coefficients in binary gaseous mixtures containing a polar and a simple component. The model has been shown to be sufficiently valid by comparison with experimental fugacity coefficients derived from gas-liquid water equilibria. Special attention has been given to the possibility of systematic experimental errors and their relevance to the validation of the equations.     

Henry's law constants and thermodynamic properties of gases and vapours in bitumens

Solubilities for 13 gases and vapours (CO₂, alkanes from ethane to n-octane, benzene, toluene, xylene, dichloromethane, and methanol) in two Alberta bitumens (Athabasca and Wolf Lake) have been measured at several temperatures (30-150°C), using gas-liquid chromatography (GLC). The GLC method yields accurate solubilities and Henry's law constants for moderately soluble gases, but is not applicable to less soluble gases such as CH₄ and H₂. Results have been used for calculations of ΔH_o and ΔC^o_p for processes of the type Solute Substance (gas) = Solute Substance (in bitumen). Correlations of Henry's law constants and ΔH^o values with carbon number for alkanes have been observed and used for predictions of CH₄ solubilities in bitumens.     

Determination of rate constants for nonequilibrium reactions in gases with participation of electrons from ballistic experiments

Investigations on determination of the rate constants for reactions in nonequilibrium processes from ballistic experiments are reviewed. We obtained and give here the constants fro dissociative recombination in air, nitrogen, argon, krypton, and xenon and also the constants for ternary recombination of Al⁺ and the attachment constants for aluminum oxides. Institute of Mechanics of Moscow State University, Moscow 119899. Translated from Fizika Goreniya i Vzryva, Vol. 33, No. 2, pp. 39–51, March–April, 1997     

Needle penetrometry with variable force loading for measuring viscosity of pelletized coal upon heating

A needle penetrometry was performed loading steady force in a range from 1×10⁻³ to 2 N to pelletized coal upon heating via a cylindrical needle. From the observed effects of shear rate on apparent viscosity of softening coal pellet, defined as the shear-rate to shear-stress ratio, it was found that the pellet behaved as a Newtonian fluid for shear rates lower than a critical one while as a pseudo-plastic fluid for higher shear rates. The penetrometry was also carried out varying the force with time. The variable force loading enabled to maintain the shear rate well below the critical one, and thereby to measure the apparent viscosity of coal pellets as Newtonian fluids over a temperature range from 600 to 800 K. Upon heating at 10 K min⁻¹, the apparent viscosity of Goonyella coal pellet decreased from about 10¹⁰ Pa s at 640 K down to a minimum of about 10⁴ Pa s at 755 K, and increased up to 10⁹ Pa s at 800 K. In a course of heating as above, the viscosity of Blind Canyon coal pellet decreased above 600 K, underwent a minimum of about 10⁶ Pa s at 715 K, and increased up to 10¹⁰ Pa s at 770 K. Decreasing the heating rate from 10 to 3 K min⁻¹ caused the minimum viscosities of the pellets to increase by 1-2 orders of magnitude.     

Evaluation of thermo‐viscosity parameters of dextran in polar and nonpolar solvent

Some thermo‐viscosity parameters like Viscosity‐molecular weight constant (K), the short‐range parameter, (A) and long‐range parameter (B) have been evaluated for the polymer “Dextran” of three different molecular weights (M?_w = 19,500, 75,000, and 250,000) in three different solvents like 6 (M) aqueous urea, 2 (M) aqueous glycine, and 50% aqueous glucose at temperatures ranging from 25 to 50°C. The study reveals that the viscosity‐molecular weight constant (K) decreases with increase in temperature for polar solvents like aqueous urea and aqueous glycine. The value of “K” increases with the rise in temperature within the range of 25 to 35°C in case of a nonpolar solvent aqueous glucose and then “K” decreases with the increase in temperature within the range of 40 to 50°C for the nonpolar solvent aqueous glucose. The short‐range parameter (A) shows the same trend as shown by “K” and the long‐range parameter “B” exhibits no definite trend with the variation of temperature. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 440–452, 2001     

Solubilities of the highly soluble gases,propane and butane,in normal paraffin and polar solvents

The solubility of highly soluble gases in both polar and non-polar solvents has been found to approach a mole fraction of unity as the solution temperature is reduced toward the normal boiling point of the dissolved gas. Solubilities of all gases in the polar solvents chlorobenzene, normal butanol and acetone, tend toward a common reference solubility for each solvent as the temperature is increased toward the solvent critical temperature. Solubilities of propane as measured in this work are reported at 0°C, 25°C and 50°C in chlorobenzene, butanol and acetone and at 25°C in hexane and hexadecane, along with solubilities of butane at 5°C, 25°C and 50°C in hexane, heptane, octane, dodecane, hexadecane and butanol. These data, along with those from literature sources, have been utilized in formulating the above generalizations.     

不同燃料SOFC的理论电池电动势及其性能

以NH₃以及3% H₂O增湿的H₂、CH₄、C₃H₈和煤炭地下气化(underground coal gasification,UCG)气为燃料,用最小Gibbs自由能法计算平衡气体组分和理论电池电动势,并测试在NiO-GDC‖GDC‖Ba_0.9Co_0.7Fe_0.2Nb_0.1O_3-δ(B_0.9CFN)阳极支撑固体氧化物燃料电池(SOFC)中的电池开路电压、电池性能和长期稳定性。结果表明,以上述气体作燃料的SOFC热力学计算理论电动势均高于1.05 V,而由于GDC电解质在还原气氛下存在电子电导,导致碳氢燃料在NiO-GDC‖GDC‖B_0.9CFN阳极支撑电池中的开路电压略小。中低温下,碳氢燃料相对缓慢的动力学过程和GDC电解质快速的氧离子传输速率,使得以UCG气、CH₄和C₃H₈为燃料的电池实际积炭比理论预测少。以UCG气为燃料的SOFC在500、550、600和650℃的最高功率密度分别高达0.151、0.299、0.537和0.729 W·cm^-2,在0.6 V恒压放电120 h后性能没有明显衰减,且阳极表面无积炭产生,表明直接UCG气SOFC具有广阔的应用前景。     

Second virial coefficients of polar gases — a correlation with stockmayer potential function

The parameters of the Stockmayer potential function were calculated by a least-squares analysis of the second virial coefficient data for 66 polar substances. By using these parameters, the second virial coefficient of these tabulated materials can be calculated with a mean standard deviation of 20.2 cm³ mole^?1 or 3.2%. The possibility of extrapolating second virial coefficients from high to low temperatures is also demonstrated.     

A test method for determining adhesion forces and Hamaker constants of cementitious materials using atomic force microscopy

A method for determining Hamaker constant of cementitious materials is presented. The method involved sample preparation, measurement of adhesion force between the tested material and a silicon nitride probe using atomic force microscopy in dry air and in water, and calculating the Hamaker constant using appropriate contact mechanics models. The work of adhesion and Hamaker constant were computed from the pull-off forces using the Johnson–Kendall–Roberts and Derjagin–Muller–Toropov models. Reference materials with known Hamaker constants (mica, silica, calcite) and commercially available cementitious materials (Portland cement (PC), ground granulated blast furnace slag (GGBFS)) were studied. The Hamaker constants of the reference materials obtained are consistent with those published by previous researchers. The results indicate that PC has a higher Hamaker constant than GGBFS. The Hamaker constant of PC in water is close to the previously predicted value C₃S, which is attributed to short hydration time (≤ 45 min) used in this study.