Isobaric thermal expansivities of mixtures ofm-cresol and quinoline from 0.1 to 400 MPa at 303 to 503 K

Isobaric thermal expansivities, α _p (p, T), of five binary mixtures ofm-cresol with quinoline (0.1499, 0.2998, 0.5005, 0.6325, and 0.8501 mol fraction ofm-cresol) were measured in a pressure-controlled scanning calorimeter over the pressure range from just above the saturation vapor pressures to 400 MPa, and at 303.15, 353.15, 403.15, 453.15, and 503.15 K. Molecular association ofm-cresol with itself and ofm-cresol with quinoline exerts large effects on the pressure and temperature behavior of α _p isotherms. The extent of association changes significantly with conditions in all except the 2∶1 mixture as demonstrated by the crossing of isotherms at lower pressures as the temperature increases. In the 2∶1m-cresol quinoline mixture the extent of association is not perturbed significantly by temperature change and the mixture behaves like a simple liquid, exhibiting a unique crossing point of α _p isotherms.     

Volumetric measurements under pressure for 2,2,4-trimethylpentane at temperatures up to 353.15 K and for benzene and three of their mixtures at temperatures up to 348.15 K

(p, V, T) data have been obtained in the form of volume ratios relative to 0.1 MPa for benzene (298.15 to 348.15 K), 2,2,4-trimethylpentane (TMP) (313.15 to 353.15 K), and their mixtures near 0.25, 0.5, and 0.75 mole fraction of benzene (313.15 to 348.15 K) for pressures up to near the freezing pressures for benzene and the mixtures, and up to 400 MPa for TMP. Isothermal compressibilitiesκ _T, isobaric expansivitie α, changes in heat capacity at constant pressureΔC _p, and excess molar volumesV ^E have been determined from the data. Literature data at atmospheric pressure have been used to convert theΔC _p toC _p at several temperatures. The isobars for α over the temperature range 278.15 to 353.15 K for TMP intersect near 47 MPa and reverse their order in temperature when plotted against pressure; normalization of the α's by dividing the values at each temperature by the α at 0.1 MPa prevents both the intersection and the reversal of the order. TheV ^E are positive and have an unusual dependence on pressure: they increase with temperature and pressure so that the order of the curves for 0.1, 50, and 100 MPa changes in going from 313.15 to 348.15 K.     

n-hexane as a model for compressed simple liquids

Isobaric thermal expansivities, _p, ofn-hexane have been measured by pressure-controlled scanning calorimetry from just above the saturation vapor pressure to 40 MPa at temperatures from 303 to 453 K and to 300 MPa at 503 K. These new data are combined with literature data to obtain a correlation equation for _p valid from 240 to 503 K at pressures up to 700 MPa. Correlation equations are developed for the saturated vapor pressure, specific volume, and isobaric heat capacity of liquid n-hexane from 240 to 503 K. Calculated volumes, isobaric and isochoric specific heat capacities. isothermal compressibilities, and thermal coefficients of pressure are presented for the entire range of pressure and temperature. The pressure-temperature behavior of these quantities is discussed as a model behavior for simple liquids without strong intermolecular interactions.     

Effect of temperature on W-shaped excess molar heat capacities and volumetric properties: Oxaalkane-nonane systems

Excess molar volumesV _m ^f of the mixtures diglyme (2,5,8-trioxanonane: TON), triglyme (2.5,8,11-tetraoxadodecane: TODD), or tetraglyme (2,5,8,11,14-pen-taoxapentadecane: POPD; E181)+n-nonane have been obtained from density measurements at 278.15, 288.15,298.15, and 308. 15 K. In addition, a micro DSC II differential scanning calorimeter was used to obtain excess molar heat capacitiesC _p ^E at constant pressure for the same mixtures except for TON+n-nonane and at the same temperatures except for 278.15 K. These results allowed us to calculate the following mixing quantities in the complete range of concentration: α(∂V _m ^υ /∂T) _p , and (∂H ^υ/∂p)nT at 298.15K. The excess molar volumes are positive with large maximum values located in the central concentration range with the exception of POPD +n-nonane at 278.15 K, which has a central miscibility gap. For these mixtures,C _p ^F has a W-shaped concentration dependence: two minima separated by a maximum.     

Viscosities of nonelectrolyte liquid mixtures. I. binary mixtures containing p-dioxane

Viscosity measurements are reported for p-dioxans with cyclohexane, n-hexane, benzene, toluene, carbon tetrachloride, tetrachloroethane, chloroform, pentachloroethane, and ethyl acetate at 303.15 K. Excess Gibbs energies of activation G ^*E of viscous flow have been calculated with Eyring's theory of absolute reaction rates. The deviations of the viscosities from a linear dependence on the mole fraction and values of G ^*E for binary mixtures have been explained in terms of molecular interactions between unlike pairs. The Prigogine-Flory-Patterson theory has been used to estimate the excess viscosity, ln , and corresponding enthalpy ln _H, entropy ln _S, and free volume ln _v terms for binary mixtures of p-dioxane with cyclohexane, n-hexane, benzene, toluene, carbon tetrachloride, and chloroform. Estimates of excess viscosities from this theory for p-dioxane with benzene, toluene, and carbon tetrachloride are good, while for the other three mixtures they are poor. The local-composition thermodynamic model of Wei and Rowley estimates the excess viscosity quite well even for p-dioxane mixtures with cyclohexane and n-hexane.     

Viscosity and density of liquid mixtures ofn-alkanes with squalane

Viscosity and density measurements are reported for binary liquid mixtures ofn-butane andn-hexane with squalane in the temperature range from 273 to 333 K. The viscosity measurements have been carried out by using a capillary viscometer calibrated with standard liquids. that is. JS5, JSIO, JS20, and water. The uncertainty in the viscosity data was estimated to be ± 1.7%. The density needed for the calculation of the viscosity has been measured by using a glass pycnometer within an accuracy of ±0.04%. In the prediction of the viscosity, the scheme of Assael et al. fails for mixtures of this type differing greatly in size.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994. Boulder, Colorado, U.S.A.     

High-performance bismuth-telluride compounds with highly stable thermoelectric figure of merit

The p-type (Bi_0.25Sb_0.75)₂Te₃ ingot doped with 8 wt% excess Te alone and the n-type Bi₂ (Te_0.94Se_0.06)₃ ingot codoped with 0.068 wt% I and 0.017 wt% Te were grown by the Bridgman method and annealed at 673 K for 5 h in a hydrogen stream. The electrical resistivity ρ, Seebeck coefficient α and thermal conductivity κ before and after annealing were measured at 298 K, so that the annealing degraded significantly ZT of the p-type specimen but enhanced remarkably that of the n-type one. The temperature dependences of ρ, α and κ of the as-grown p-type and annealed n-type specimens with higher ZT were investigated in the temperature range from 200 to 360 K. As a result, ZT values of the as-grown p-type and annealed n-type specimens have a broad peak and reached great values of 1.19 and 1.13 at approximately 320 K, respectively. The present materials were thus found to be far superior to any other bismuth-telluride compound in the thermal stability of energy conversion efficiency in addition to the high performance.     

Reaction sintering and the α-Si3N4/β′-sialon transformation for compositions in the system Si-Al-O-N

The reaction sintering of three powder compositions corresponding to points near theβ′-phase line in the region of z=0.75 has been studied using apparatus which allowed the continuous monitoring of the densification kinetics. The powder compositions were prepared from mixtures ofα-Si₃N₄, Al₂O₃ and AIN, and the weight changes in the compacts could be kept to less than ∼ 1% over a two hour period. The densification rate is sensitive to small changes in powder composition and decreases markedly as theβ∼'-sialon phase is approached from the oxygen-side. Theα-Si₃N₄ toβ′-sialon conversion rate, on the other hand, is almost independent of the powder composition. The sintering and transformation kinetic data, combined with surface area measurements and observations on the microstructure of the sintered compacts, indicate that the sintering behaviour is controlled by at least two processes, namely the vapour phase transport of material and a solution-diffusion-reprecipitation process involving a grain boundary liquid phase. Both processes result in the conversion ofα-Si₃N₄ toβ′-sialon and result in microstructural coarsening but only the second process leads to overall densification in the powder compact.     

Determination of optical constants of CdS x Se y electrodeposits

The optical constantsn(λ) and α(λ) have been determined for CdS_xSe _y films electrodeposited on to glass doped with SnO₂. From a (αhv)² versus photon energy plot, a value for the direct band gap of the electrodeposited polycrystalline semiconductor ofE _g=1.83 eV was obtained, which indicates a low proportion of S²⁻ in the thin films formed.     

Viscosity and thermal conductivity of binary n-heptane + n-alkane mixtures

New absolute measurements of the viscosity of binary mixtures of n-heptane with n-hexane and n-nonane are presented. The measurements, performed in a vibrating-wire instrument, cover a temperature range 290–335 K and pressures up to 75 MPa. The concentrations studied are 40 and 70% by weight of n-heptane. The accuracy of the reported viscosity data is estimated to be ±0.5%. The present measurements, together with other n-heptane + n-alkane viscosity and thermal-conductivity measurements, are used to develop a consistent semiempirical scheme for the correlation and prediction of these mixture properties from those of the pure components.     

Empirical and Semi-theoretical Methods for Predicting the Viscosity of Binary <Emphasis Type="Italic">n</Emphasis>-Alkane Mixtures

In this study, empirical and semi-theoretical methods for predicting the viscosity of binary mixtures of n-alkanes are presented at atmospheric pressure and in the temperature range from 288 to 333 K. In the empirical viscosity calculation method, a modified version of the Andrade equation and a simple mixture rule are used. The proposed semi-theoretical method employs both the Enskog’s hard-sphere theory for dense fluids and the principle of corresponding states. The viscosities of binary mixtures of n-heptane with n-hexane and n-nonane covering different compositions were calculated using these methods which require only critical properties and the normal boiling point as input data. The predictions were compared with accurate experimental data in the literature. Highly satisfactory results were obtained. The percent average absolute deviations amount to 1.2 and 0.9% utilizing the empirical and semi-theoretical viscosity methods, respectively, for 27 data points. Paper presented at the Fifteenth Symposium on Thermophysical Properties, June 22–27, 2003, Boulder, Colorado, U.S.A.     

Conduction in Mn substituted Ni-Zn ferrites

The d.c. electrical resistivity ‘ρ’ and thermoelectric power ‘α’ are studied as a function of temperature for Mn substituted ferrites with general formula Zn_0·3Ni_0·7+x Mn _x Fe_2−2x O₄. At lower Mn concentrations, the increase in d.c. resistivity is attributed to the hindering of Verwey mechanism Fe²⁺ ⇌ Fe³⁺ due to stable bonds of Mn³⁺ + Fe²⁺ pair. The decrease in resistivity at higher Mn concentrations (i.e. whenx > 0·15) is attributed to the formation of Mn³⁺ cluster and Ni²⁺ ⇌ Ni³⁺. The activation energy values show one to one correspondence with resistivity values. The compositional variation of thermoelectric power showsn-type behaviour for the samples withx < 0·2 whereasp-type behaviour for the samples withx ⩾ 0·2. Thep −n transition is attributed to the formation of Ni³⁺, Fe²⁺ + vacancies which act asp-type carriers. The temperature dependences ofα, ρ, and mobility clearly confirm the conduction mechanism to be due to polaron hopping.     

Composition dependence of binary diffusion coefficients in alkane mixtures

The binary diffusion coefficients of mixtures of n-heptane with n-hexane and 2,2,4-trimethylpentane with n-hexane have been measured at various compositions at 308.1, 312.2, and 316.5 K using the Taylor dispersion technique. The experimental results for the n-hexane/n-heptane system were in good agreement with the literature values (<1.5%). The observed binary diffusion coefficients for this system exhibit a linear dependence on composition. On the contrary, the results of the n-hexane/2,2,4-trimethylpentane system reveal an interesting behavior of the composition dependence of the binary diffusion coefficients, presenting a slight maximum, for composition at a molar fraction of n-hexane of 0.86. In order to explain this difference in behavior, the influence of branching of molecules on diffusion is discussed. It was found that although the Enskog hard-sphere model for binary diffusion can reproduce the experimental results for the n-hexane/n-heptane system within 3%, it failed to predict the composition dependence of the n-hexane/2,2,4-trimethylpentane system within the experimental accuracy. The results showed that there is significant effect of branching in alkane molecules on the diffusion coefficient. This effect has been quantified using the roughness parameter, which represents the magnitude of coupling between translational and rotational motions.     

Enhancement of the Seebeck coefficient in touching M/Bi–Te/M (M = Cu and Ni) composites

The resultant Seebeck coefficient α of the touching p- and n-type M/Bi–Te/M (M = Cu and Ni) composites was measured as a function of z at a scan step of 0.5 mm using thermocouples set at three different intervals of s = 4, 6.5 and 8 mm, where s is the interval between two probes and z is the distance from the center of Bi–Te compound to the middle of two thermocouples. Bi–Te compounds have a thickness of t _Bi–Te = 6 mm but the thickness t _M of both end metals sandwiching their compounds was varied from 0.5 mm to 6 mm. The composites were compacted tightly at a force of about 10 N by a ratchet. When two probes are placed on both end metals, the resultant α was significantly enhanced and exhibited a tendency to increase as s approaches t _Bi–Te, like the welded composites. The enhancement in α is attributed to the contribution from the barrier thermo-emf generated near the interface. When the thickness t ₀ of metal outside two probes set at s = 6.5 mm was increased from 0.25 mm to 5.75 mm, the averaged α for M = Cu and Ni was increased by 3.8% in the p-type composite, while reversely it was decreased by 4.8% in the n-type one. It was first observed that t ₀ also has a significant influence on the resultant α. The maximum α of the p- and n-type Ni/Bi–Te/Ni composites then reached great values of 264 μV/K at t _M = 6 mm (corresponding to t ₀ = 5.75 mm) and −280 μV/K at t _M = 1.2 mm (corresponding to t ₀ = 0.95 mm), respectively, which are 29% and 23% larger in absolute value than their intrinsic α values. These maximum α were barely changed with time. It was thus found that the barrier thermo-emf is generated steadily even in touching composites and the resultant α is highly sensitive to the position of leads connected to the metal electrode of a thermoelement.     

Speed-of-Sound Measurements in n-Nonane at Temperatures between 293.15 and 393.15 K and at Pressures up to 100 MPa

Speed-of-sound measurements in liquid phase n-nonane (C₉H₂₀) are reported along six isotherms between 293.15 and 393.15 K and at pressures up to 100 MPa. The experimental technique is based on a double reflector pulse-echo method. The acoustic path lengths were obtained by comparison with measurements carried out at atmospheric pressure and ambient temperature in pure water. The values of the speed of sound are characterized by an overall estimated uncertainty of less than 0.2 %. These results were compared with literature values and with predictions of a dedicated equation of state.Paper presented at the Seventeenth European Conference on Thermophysical Properties, September 5–8, 2005, Bratislava, Slovak Republic.     

Viscosity of binary mixtures. IV. Triethylamine with alkanes and monoalkylamines at 303.15 and 313.15 K

Viscosities and densities of seven binary mixtures of n-hexane, n-octane, isooctane, n-propylamine, n-butylamine, n-hexylamine, and n-octylamine with triethylamine have been measured at 303.15 and 313.15 K. Deviations of viscosities from a linear dependence on the mole fraction and values of excess Gibbs energy of activation G ^*E of viscous flow are attributable to the H-bonding and to the size of the alkylamine and alkane molecules.     

The viscosity of five liquid hydrocarbons at pressures up to 250 MPa

This paper reports new measurements of the viscosity of toluene, n-pentane, n-hexane, n-octane, and n-decane at pressures up to 250 MPa in the temperature range 303 to 348 K. The measurements were performed with a vibrating-wire viscometer and with a relative method of evaluation. Calibration of the instrument was carried out with respect to reference values of the viscosity of the same liquids at their saturation vapour pressure. The viscosity measurements have a precision of ±0.1% but the accuracy is limited by that of the calibration data to be ±0.5%. The experimental data have been represented by polynomial functions of pressure for the purposes of interpolation. The data are also used as the most precise test yet applied to a representation of the viscosity of liquids based upon hard-sphere theory.     

Measurements of the Liquid Viscosities of Mixtures of n-Butane, n-Hexane, and n-Octane with Squalane to 30 MPa

The viscosities of liquid mixtures of n-butane, n-hexane, and n-octane with squalane that represent model mixtures of refrigerants with refrigeration oil were measured at temperatures between 273.15 and 333.15 K, and at pressures from 0.1 to 30 MPa, by using a falling body viscometer. The uncertainty of the measurements was estimated to be no larger than 2.9%. The experimental viscosity values were fitted to a Tait-like equation within 2.8%. There are larger deviations between the experimental data and calculated values predicted by the equation of Kanti et al., which is derived from the Flory theory. By introducing an interaction parameter of the energetic mixing rule into the equation, the deviations were significantly reduced.     

Enzyme-catalyzed preparation of supramolecular structured hydrogel of polypseudorotaxanes derived from the self-assembly of α-CDs with 3-arm p-hydroxyphenylpropionate terminated PEG

A kind of novel 3-D cross-linked supramolecular structured hydrogels has been fabricated via enzymatic oxidative coupling of polypseudorotaxanes (PPRs) derived from the self-assembly of α-cyclodextrins (α-CDs) with 3-arm p-hydroxyphenylpropionate terminated PEG (3-HPPP) as a macromer by using horseradish peroxidase (HRP)/H₂O₂ catalytic system. The enzymatic cross-linking of the macomer or PPRs made with a smaller amount of α-CDs was found to be much faster than that by ordinary chemical pathways, showing the promise to be used as the surgical adhesive and sealant which are needed to rapidly function in vivo. The gelation time was highly extended and the gel content was considerably decreased by increasing the α-CDs to macromer feeding molar ratio. Thereby these hydrogels exhibited a decreasing trend in dynamical mechanical properties with increasing the amount of α-CDs in regard to the blank hydrogel made without α-CD addition.     

Thermal expansion of lead silicate glasses

The thermal expansion, when heated from 77 to 273 K, of two samples of lead silicate glass, containing 21 and 28.5 mol % PbO, has been measured. The temperature dependence of the thermal expansion coefficient,α, is in qualitative agreement with the expansion behaviour of sodium silicate glass. However, the addition of ∼ 21 mol % PbO to silica is required to produce an increase in the magnitude ofα comparable to the addition of only ∼ 10 mol % Na₂O. The differences in the magnitudes ofα for lead and soda glasses are considered in the right of previous proposals for their structures.