Correlation of high-pressure diffusion and viscosity coefficients for n-alkanes

Self-diffusion coefficient and viscosity coefficient data for liquid n-alkanes over the whole pressure range at different temperatures are satisfactorily correlated simultaneously by a method which is just an extension of that previously used to apply the smooth hard-sphere theory of transport properties to individual transport coefficients. Universal curves are developed for reduced quantities D ^* and ^* as a function of reduced volume. A consistent set of values is derived for the characteristic volume V ₀ and for parameters R _D and R , introduced to account for effects of nonspherical molecular shape and molecular roughness. On this basis, accurate calculation can be made of self-diffusion and viscosity coefficients for other members of the n-alkane series, for which data are at present limited.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

Correlation and prediction of dense fluid transport coefficients. I. n-alkanes

Recent accurate measurements of the self-diffusion coefficient for n-hexadecane and n-octane and of the viscosity coefficient for n-heptane, n-nonane, and n-undecane over wide pressure ranges have been used to provide a critical test of a previously described method, based on consideration of hard-sphere theory, for the correlation of transport coefficient data. It is found that changes are required to the universal curve for the reduced viscosity coefficient as a function of reduced volume and, also, to the parameters R _D, R , and R which were introduced to account for effects of nonspherical molecular shape. The scheme now accounts most satisfactorily for the self-diffusion, viscosity, and thermal conductivity coefficient data for all n-alkanes from methane to hexadecane at densities greater than the critical density.     

Application of rough hard-sphere theory to diffusion in n-alkanes

Tracer diffusion coefficients are reported for n-alkane solutes in n-dodecane, n-eicosane, n-eicosane, and n-octacosane in the temperature range 304–533 K at 1.38 MPa. Rough hard-sphere theory is used to interpret the data. The translational-rotational coupling parameters are determined for each solute-solvent pair at each temperature. The nature of the coupling parameter and the possibility of relating it to molecular properties and temperature in a homologous series are discussed.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

Thermal conductivity of liquid n-alkanes

The thermal conductivity of liquids has been shown in the past to be difficult to predict with a reasonable accuracy, due to the lack of accurate experimental data and reliable prediction schemes. However, data of a high accuracy, and covering wide density ranges, obtained recently in laboratories in Boulder, Lisbon, and London with the transient hot-wire technique, can be used to revise an existing correlation scheme and to develop a new universal predictive technique for the thermal conductivity of liquid normal alkanes. The proposed correlation scheme is constructed on a theoretically based treatment of the van der Waals model of a liquid, which permits the prediction of the density dependence and the thermal conductivity of liquid n-alkanes, methane to tridecane, for temperatures between 110 and 370 K and pressures up to 0.6 MPa, i.e., for 0.3T/T _c0.7 and 2.4P/P _c3.7, with an accuracy of ±1%, given a known value of the thermal conductivity of the fluid at the desired temperature. A generalization of the hard-core volumes obtained, as a function of the number of carbon atoms, showed that it was possible to predict the thermal conductivity of pentane to tetradecane±2%, without the necessity of available experimental measurements.     

Correlation and prediction of dense fluid transport coefficients. III. n-alkane mixtures

Viscosity and thermal conductivity coefficients for binary, ternary, and quaternary n-alkane mixtures are predicted over extended ranges of temperature and pressure, in excellent agreement with experiment, by extension of a method recently described for the correlation of n-alkane transport coefficients. The outstanding advantage of this approach is that there are no adjustable parameters. Furthermore, in contrast with other mixture viscosity equations, this scheme does not require experimental viscosity coefficient data for the pure components under the same conditions of temperature and pressure.     

Correlation of dense fluid self-diffusion,shear viscosity,and thermal conductivity coefficients

A general procedure has been developed for simultaneously fitting any two of the self-diffusion coefficient, the viscosity (as the fluidity), and the thermal conductivity (as its reciprocal) as Dymond reduced coefficients, (D*,*,*), to a simple function of the volume and the temperature for dense fluids. For example,D*=₁+₂ V _r/(1+₃,/V _r), whereV _r=V[1-₁(T–T _r)-₂(T–T _r)²].T _r is any convenient temperature, here 273.15 K. AsV _r is common to the two properties, only eight coefficients, _j and _k are required. Such reduced transport-coefficient curves are geometrically similar for members of groups of closely related compounds. The procedure has been extended to give family curves for such groups by fitting a pair of transport properties for three substances from the group in a single regression. Overall, fewer coefficients are required than for other schemes in the literature, and the fitting functions used are simpler. The curves so constructed can be used for the correlation of data obtained from different sources, as well as interpolation and, to a limited extent, extrapolation. A comparison is made for a number of compotmd groups between simultaneous fits of the pairs (D– ), (D–), and (–)Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

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.     

Correlation and prediction of dense fluid transport coefficients. V. Aromatic hydrocarbons

A previously described method, based on consideration of hard-sphere theory, is used for the simultaneous correlation of the coefficients of self-diffusion, viscosity, and thermal conductivity for benzene, toluene, o-, m-, and p-xylene, mesitylene, and ethylbenzene in excellent agreement with experiment, over extended temperature and pressure ranges. Values are given for the roughness factors R _D , R , and R , and the characteristic volume, V ₀, is expressed as a function of both carbon number and temperature.     

The transport properties of ethane. II. Thermal conductivity

A new representation of the thermal conductivity of ethane is presented. The representative equations are based upon a body of experimental data that have been critically assessed for internal consistency and for agreement with theory in the zero-density limit and in the critical region. The representation extends over the temperature range from 100 K to the critical temperature in the liquid phase and from 225 K to the critical temperature in the vapor phase. In the supercritical region the temperature range extends to 1000 K for pressures up to 1 MPa and to 625 K for pressures up to 70 MPa. The ascribed accuracy of the representation varies according to the thermodynamic state from ±2% for the thermal conductivity of the dilute gas near room temperature to ±5% for the thermal conductivity at high pressures and temperatures. Tables of the thermal conductivity, generated by the relevant equations, at selected temperatures and pressures and along the saturation line are also provided.     

The thermal conductivity of n-hexane,n-heptane,and n-decane by the transient hot-wire method

New absolute measurements of the thermal conductivity of liquid n-hexane, n-heptane, and n-decane are reported. The measurements have been carried out in the temperature range 300–370 K at atmospheric pressure in a transient hotwire instrument. The accuracy of the measurements is estimated to be ±0.5%. The density dependence of the thermal conductivity of n-hexane and n-heptane is found to be well described by a universal equation for the hydrocarbons based on a rough hard-sphere model. The measurements of the three hydrocarbons studied are also employed to generate more accurate effective core volumes, which are the only parameters characteristic of the fluid required for the application of the proposed universal scheme.     

The thermal conductivity and viscosity of benzene

New absolute measurements of the thermal conductivity of liquid benzene are reported. The measurements have been carried out in the temperature range 295–340 K, at atmospheric pressure, in a transient hot-wire instrument. The accuracy of the measurements is estimated to be ±0.5%. The measurements presented in this paper have been used, in conjunction with other high-pressure measurements of thermal conductivity and viscosity, to develop a consistent theoretically based correlation for the prediction of these properties. The proposed scheme permits the density dependence of the thermal conductivity and viscosity of benzene, for temperatures between 295 and 375 K and pressures up to 400 MPa, to be represented successfully by two equations containing just two parameters characteristic of the fluid at each temperature.     

The transport coefficients of polyatomic liquids

The paper presents the results of a preliminary attempt to represent both the viscosity and the thermal conductivity of normal alkanes in the liquid phase by means of a mutually consistent scheme. The correlation method proposed is based upon the general results of the hard-sphere theory of dense fluids, although it does not make use of the detailed predictions of that model. It is shown that the viscosity of the alkanes, ethane, propane, n-butane, n-hexane, and n-octane may be represented by a single, universal function of reduced volume if each species is assigned a characteristic molar volume which is but weakly temperature dependent. Using the same values of molar volume the thermal conductivity of the same fluids can be represented by a further universal function of reduced volume by means of the choice of a second, temperatureindependent parameter.Paper presented at the Ninth Symposium on Thermophysical Properties, June 24–27, 1985, Boulder, Colorado, U.S.A.     

Correlation and prediction of dense fluid transport coefficients. IV. A note on diffusion

Recent accurate calculations of the corrections to Enskog theory for hard-sphere diffusion have resulted in a revision of the hard-sphere based correlation for dense fluid transport coefficients. The expression previously given for. the reduced diffusion coefficient in terms of reduced volume is adjusted in line with these values. No changes are required to the characteristic volumes but the roughness factors are reduced. Of particular note is the fact that methane now corresponds to a rough hard-sphere system.     

Thermal conductivity of n-tridecane at pressures up to 500 MPa in the temperature range 35–75°C

Thermal conductivity coefficients are reported for liquid n-tridecane along three isotherms, 35, 48, and 73°C, and for pressures from 20 to 500 MPa. The measurements have been made with a transient hot-wire instrument, and the results, when corrected for the effects of radiation absorption, have an estimated uncertainty of ±0.7%. The thermal conductivity as a function of density along isotherms can be represented by means of the same form of equation as that found suitable for other normal alkanes, and this is based upon a heuristic modification of the van der Waals theory of liquids.     

Simultaneous measurement of the thermal conductivity and thermal diffusivity of liquids

In theory, the hot-wire technique for measuring the thermal conductivity of liquids can be used simultaneously to determine the thermal diffusivity. In practice, however, the latter property has so far been determined only with moderate accuracy because of (a) inaccurate bridge balancing due to drift problems, (b) parasitic capacities that delay the heating, and (c) poor precision in the determination of the time. A new measurement procedure has been developed which features (a) a short measuring time, (b) a reduced significance of the balancing technique, (c) a good reproducibility, and (d) a low sensitivity to most error sources. Thermal conductivity and thermal diffusivity results using this procedure, for toluene and n-heptane, which are the generally accepted standards for thermal conductivity, are presented and compared with results from other sources.     

Mutual diffusion coefficients for two n-octane isomers in n-heptane

A new instrument for the measurement of mutual diffusion coefficients in the liquid phase based on the Taylor dispersion technique has been developed. The instrument design and operation are described. The working region of the instrument has been established using an ideal model for the apparatus. The necessary design considerations and corrections to ensure that the instrument operates in accordance with the theory of the method are discussed. The accuracy of the experimental results is estimated to be ±1%. Experimental data for n-octane and 2,2,4-trimethylpentane at infinite dilution in n-heptane are reported. Correlation schemes based on the rough-hard sphere theory have been used to represent the experimental data and their predictive capability examined.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

Correlation and prediction of dense fluid transport coefficients. VI.n-alcohols

A previously described method, based on considerations of hard-sphere theory, is used for the simultaneous correlation of the coefficients of viscosity, self-diffusion, and thermal conductivity for then-alcohols, from methanol ton-decanol, in excellent agreement with experiment, over extended temperature and pressure ranges. Generalized correlations are given for the roughness factors and the characteristic volume. The overall average absolute deviations of the experimental viscosity, self-diffusion, and thermal conductivity measurements from those calculated by the correlation are 2.4, 2.6, and 2.0%, respectively. Since the proposed scheme is based on accurate density values, a Tait-type equation was also employed to correlate successfully the density of then-alcohols. The overall average absolute deviation of the experimental density measurements from those calculated by the correlation is ±0.05%.     

The viscosity of gaseous propane and its initial density dependence

Results of five series of high-precision viscosity measurements on gaseous propane, each differing in density, are reported. The measurements were performed in a quartz oscillating-disk viscometer with small gaps from room temperature up to about 625 K and for densities between 0.01 and 0.05 mol · L^–1. The experimental data were evaluated with a first-order expansion, in terms of density, for the viscosity. Reduced values of the second viscosity virial coefficients deduced from the zero-density and initial-density viscosity coefficients for propane and for furthern-alkanes are in close agreement with the theoretical representation of the Rainwater-Friend theory for the potential parameter ratios by Bich and Vogel. A new representation of the viscosity of propane in the limit of zero density is provided using the new experimental data and some data sets from literature. The universal correlation based on the extended principle of corresponding states extends over the temperature range 293 to 625 K with an uncertainty of ±0.5 % and deviates from earlier representations by about 1 % at the upper temperature limit.     

填料粒子形貌对液态灌封胶粘度与热导率的影响

采用40μm球形与无规则形α-Al2O3粒子填充液体硅橡胶,研究了Al2O3粒子用量、形貌对液态灌封胶的粘度与热导率的影响,并用XRD、SEM分析了两种Al2O3的晶型以及在灌封胶中的分布状态。结果表明,在相同的填充量下无规则形Al2O3粒子填充灌封胶的热导率高,球形Al2O3填充灌封胶的可加工性优异。当球形与无规则形填料混合填充的比例为9∶1时可以获得最高的热导率,比单一使用球形Al2O3提高了17.1%。     

The thermal conductivity of n-hexadecane+ ethanol and n-decane+butanol mixtures

New absolute measurements, by the transient hot-wire technique, of the thermal conductivity of n-hexadecane and binary mixtures of n-hexadecane with ethanol and n-decane with butanol are presented. The temperature range examined was 295–345 K and the pressure atmospheric. The concentrations of the mixtures studied were 92% (by weight) of n-hexadecane and 30 and 70% (by weight) of n-decane. The overall uncertainty in the reported thermal conductivity data is estimated to be ±0.5%, an estimate confirmed by the measurement of the thermal conductivity of water. A recently extended semiempirical scheme for the prediction of the thermal conductivity of mixtures from the pure components is used to correlate and predict the thermal conductivity of these mixtures, as a function of both composition and temperature.