Infinite dilution activity coefficents of hydrocarbons in tetra-n-alkyltin solvents between 40 and 60°C measured by gas-liquid chromatography

Infinite dilution activity coefficients for twenty-three hydrocarbons in tetra-n-amyltin (TAT) and in tetra-n-lauryltin (TLT) at several temperatures between 40 and 60°C were measured by gas liquid chromatography. The results, together with those obtained in an earlier paper in tetra-n-octyltin (TOT), are compared and discussed in terms of the equation of state theory of Flory and of the lattice fluid theory of Sanchez and Lacombe.     

Thermodynamics of tri-n-octyltin chloride+hydrocarbon mixtures by gas-liquid chromatography

Gas liquid chromatography was employed to measure the activity coefficients of a group of hydrocarbons at infinite dilution in tri-n-octyltin chloride at 40, 45, 50, 55 and 60°C. The partial molar excess thermodynamic quantities are interpreted by means of the Flory-Patterson theory, and compared with the results obtained for the same group of solutes in tetra-n-octyltin as the solvent. The alkanes activity coefficients and excess enthalpies in both phases are linearly related. Enthalpyentropy compensation in both solvents is discussed.     

Viscosity studies of solutions of water inn-aliphatic alcohols at various temperatures

Viscosity measurements have been made at 25°C on solutions of water inn-propanol, and at 15, 25, 35, and 45°C on solutions of water inn-butanol,n-pentanol, andn-hexanol over the respective solubility ranges. For most of the systems, water decreases the viscosity of the dry alcohols, while for the lower members of the series literature data report an increase in viscosity on addition of water. These results are rationalized in terms of two kinds of interaction between water molecules and alcohols: participation of water molecules in chain formation for the lower alcohols and formation of water-centered complexes for butanol and higher alcohols.     

Model systems for hydrophobic interactions: Volumes and heat capacities ofn-alkoxyethanols in water

The densities and heat capacities of the first four members of the 2-n-alkoxyethanols were measured in water over the whole mole fraction range with a flow densimeter and a flow microcalorimeter. The methoxy and n-propoxy homologs were studied at 25°C, ethoxyethanol at 19, 25, and 40C, andn-butoxyethanol at 4, 10, 25, 40, and 55°C. While methoxyethanol behaves as a fairly typical polar nonelectrolyte in water,n-butoxyethanol shows trends in the concentration dependence which resemble micellization; some pseudo-microphase transition occurs at about 0.02 mole fraction, and this transition concentration decreases with increasing temperature. There is no simple relationship between this phenomenon and the existence of a lower critical solution temperature at 49°C since the sharpness of the thermodynamic changes is maximum at the lowest temperature and at 55°C the apparent molal quantities on both sides of the two-phase region appear to fall on the same continuous curve. In the region prior to the pseudo-microphase separation the apparent and partial molal heat capacities decrease regularly but beyond approximately 0.01 mole fraction increase sharply to a maximum, suggesting some type of pre-association. The apparent molal heat capacity of water in the binary solutions is larger than the molar heat capacity of water over the whole mole fraction range. The present data seem to be consistent with a clathrate model for hydrophobic hydration and interactions with these systems.     

Thermal conductivity ofn-Tetracosan around the liquid-liquid transition temperatureT u

Forn-Tetracosan the temperature dependence of the thermal conductivity has been determined between 52 °C and 150 °C by the transient hot strip method. A decreasing thermal conductivity is followed by a constant one forT100 °C.The change in slope can be well estimated by using data of Brillouin scattering and specific volume measurements thus confirming the existence of theT _u -phenomenon.     

Thermodynamics of Tetra-n-octyltin+ hydrocarbon systems by gas-liquid chromatography

The activity coefficients of fifteen hydrocarbons at infinite dilution in tetra-n-octyltin were measured using gas-liquid chromatography at five temperatures between 40 and 60°C. Partial molar excess thermodynamic properties are calculated from the experimental results, and discussed within the framework of the equation of state theory of Flory and of the Ising fluid theory of Sanchez and Lacombe. Both theories results in binary mixture characteristic parameters (X₁₂ and P^*, respectively) that decrease linearly with the temperature. The results may be interpreted by assuming that there is orientational order in pure tetra-n-octyltin and in pure n-alkanes, but not in the remaining solutes; the destruction of this order on mixing the hydrocarbons with the tin compound results in important contributions to the excess thermodynamic properties.     

Molar volumes ofn-alcohols from 15 to 80°C

Densities of seven even carbon number n-alcohols from 1- hexanol to 1-octadecanol from 15 to 80°C were determined at 5° intervals. The density was found to be a linear function of the temperature within this temperature range. A simple equation which correlates teh molar volume with the carbon number and temperature of the alcohols is presented. Excellent agreements between the calculated, measured, and literature values were obtained. Accurate predictions of the molar volume and hence the density of the n-alcohols from 1-propanol to 1-octadecanol including the odd carbon number 1-alcohols in the temperature range studied can be made using the equation.     

Molecular association ofn-alcohols in nonpolar solvents. excess volumes and viscosities ofn-pentanol+n-octane mixtures at 0, 5, 25, 35 and 45°C

Densities and viscosities of n-pentanol +n-octane mixtures in the temperature range 0 to 45°C are reported. The data are discussed in terms of molar excess volumes, molar excess fluidities and molar excess activation energies of viscous flow in order to obtain structural information of the mixtures. It is shown that the structural modifications of n-pentanol and n-octane upon mixing, significantly contribute to the parameters governing the viscous flow and the volume of the mixtures.     

Activation of low-percentage Re-Al2O3 and Tc-Al2O3 catalysts for the dehydrogenation of paraffins

The activity and selectivity of low-percentage (0.1–1 mass. %) Re-Al₂O₃ and Tc-Al₂O₃ catalysts in the dehydrogenation ofn-dodecane is shown to increase in response to an increase in the temperature of their activation in hydrogen from 500°C to 900°C. The activities of such catalysts are comparable to those of analogous alumina-platinum systems, while the selectivity of the former catalysts inn-monoolefin production is higher than that of the latter.Deceased January 7, 1991.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 484–487, March, 1993.     

Halomethanes in tri-n-octylamine and squalane mixtures at infinite dilution

The retention behavior of eight halomethanes and four saturated hydrocarbons was measured in gas chromatographic stationary phases consisting in tri-n-octylamine (TOA), squalane (SQ) and six TOA+SQ mixtures, at 55.0, 58.5, 62.5 and 65.0°C. Equlibrium constants for complex formation were extracted from experimental data by using a lattice model developed by Martire. The results may be interpreted in terms of the formation of weak hydrogen-bonded complexes, with sociation constants of about 0.13 L-mol^–1 for haloforms and 0.07 L-mol^–1 for dihalomethanes at 60°C.     

Viscosities ofn-alkylamines from 15 to 80°C

The viscosities of seven n-alkylamines from n-butylamine to n-decylamine were determined from 15 to 80°C at 5°C intervals. The intrinsic volumes were determined by extrapolation of the plot of fluidity against molar volume to zero fluidity and found to be a linear function of the number of carbon atoms. Plots of the logarithm of viscosity vs. reciprocal absolute temperature were almost linear. The energies of activation for viscous flow for the n-alkylamines were calculated and found to increase with increase in the carbon number. The B values, based on Hildebrand's equation and representing a measure of a molecules resistance to transport of momentum, were calculated for each of the n-alkylamines. A modified form of the equation describing the change fluidity with temperature was then formulated. It is suggested that the activation energy for viscous flow consists of the sum of the energy required for the expansion of the void volume and the energy required to overcome intermolecular interactions. These energies were calculated and discussed.     

A small-angle neutron scattering study of the ethyl (n-octyl) phosphate micelles in water

Summary Mixed-double chain anionic surfactants, barium- and lithium-salts of ethyl(n-octyl) phosphate (EOP), which are asymmetric in the molecular shape, and a series of identical chain di-n-alkyl phosphate lithium salts have been synthezized. The limiting partial molar volume of a PO ₄ ^– group (23.43±0.41 cm³ mol^–1) for use in small-angle neutron scattering analysis was determined by density measurements of a series of identical chain di-n-alkyl phosphate lithium salts. For lithium EOP-D₂O system, a critical micellar concentration (2.3 wt%) was determined by³¹P NMR spectra. The micellar shape and size in the EOP-water binary system has been investigated by using small-angle neutron scattering (SANS) spectra. It has been found that the micelles of barium EOP in water have the shape of a prolate spheroid and aggregation numbers (n) equal to 48 at 23°C and 52 at 50°C. For the lithium EOP-micellar system, it has been found that the minimum micelle with an aggregation numbern=21 is spherical and micellar growth and variation from the spherical to the prolate shape might occur with an increase in concen tration above the CMC.     

Standard molar enthalpies,volumes, and heat capacities of adamantane in cyclohexane,n-hexane,and carbon tetrachloride. Interpretation using the scaled-particle theory

The volumes, heat capacities, and enthalpies of solution of adamantane in cycloxane,n-hexane, and carbon tetrachloride have been measured as a function of concentration at 25°C (15, 25, and 35°C for the volumes). The results extrapolated to infinite dilution have been resolved into cavity formation and interaction terms. The former have been calculated from the equations of the scaled-particle theory. To estimate the contribution from the latter, we have assumed some proportionality between adamantane-solvent and cyclohexane-solvent interactions. This assumption has been verified with the three different solvents for the three studied thermodynamic functions. The diameter of adamantane in solution has been determined to be 6.36 Å.     

Excess enthalpies of ethylbenzene + alkane systems at 25°C. An interpretation in terms of the Prigogine-Flory-Patterson model

The molar excess enthalpies for the ethylbenzene + n-decane and ethylbenzene + n-tetradecane systems have been measured at 25°C over the complete concentration range. These results and others from the literature for alkanes + ethylbenzene, and alkanes + toluene have been discussed in terms of the Prigogine-Flory-Patterson theory.     

Excess thermodynamic properties of binary liquid mixtures containing dimethylsulfoxide at 30°C

The exess volumes of mixing of dimethylsulfoxide with n-, sec- and tertbutylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and cyclohexylamine have been measured as a function of composition at 30°C by a dilatometric method. For all amines V^E values are negative over the entire mole fraction range. The results are attributed to the interaction between unlike molecules.     

Excess Enthalpies of 2,2-Dimethylbutane + Cyclohexane + (Octane or Dodecane) at 25°C

Measurements of excess molar enthalpies at 25°C in a flow microcalorimeter,are reported for the two ternary mixtures 2,2-dimethylbutane + cyclohexane +n-octane and 2,2-dimethylbutane + cyclohexane + n-dodecane. Smoothrepresentations of the results are described and used to construct constant enthalpy contourson Roozeboom diagrams. It is shown that useful estimates of the ternary enthalpiescan be obtained from the Flory theory using only the physical properties of thecomponents and their binary mixtures.     

Viscosities of long chainn-alcohols from 15 to 80°C

Viscosities of five n-alcohols from 1-hexanol to 1-tetradecanol were determined from 15 to 80°C at 5°C intervals. Plot of the logarithm of viscosity vs. reciprocal absolute temperature were almost linear. The energies of activation for viscous flow were determined for each of the alcohols and found to increase with increase in chain length. The intrinsic molar volumes V_o were determined by extrapolation to zero fluidities. The fluidities of the alcohols were found to obey the equation

Cubic structure II double clathrate hydrates with tetra(n-propyl)ammonium fluoride

A double clathrate hydrate with the composition THF·0.5(n-Pr)₄NF·16H₂O and cubic structure II (CS-II,a=17.67 Å) has been obtained. Its experimental density is 1.053±0.001 g/cm³; its melting point is 8.1°C, i.e. 3.1°C higher than that of the THF·17H₂O hydrate. The double hydrates of acetone, 1,4-dioxan, trimethyleneoxide and 1,3-dioxolane with (n-Pr)₄NF have melting points of –14.8, –5.5, –2.6 and –9.6°C, respectively. With pressure increase up to 6 kbar the melting points of the double hydrates increase monotonously in contrast to common CS-II hydrates. The friability of the structure of the hydrates (the packing coefficient) and their sensitivity to pressure (dT/dP) are compared.The results of this work have been reported at the International Seminar on Inclusion Compounds, Jaszowiec (Poland), 24–26th September 1987.     

Calorimetric study on the solubilization of some primary alcohols by reversed AOT micelles

A calorimetric method to evaluate, at the same time, the distribution constant and the standard enthalpy of transfer of a solute partitioned between organic phase and reversed micelles is proposed. The method was applied to the partition of methanol, 1-propanol and 1-pentanol between n-heptane and AOT reversed micelles containing water at 25°C. The results show that the distribution constant decreases as the alcohol alkyl chain length increases and that the solubilization site can change as the water content of reversed AOT micelles increases. In particular, at sufficiently high water content, methanol seems to be preferably solubilized in the aqueous pseudophase whereas 1-pentanol prefers always the palisade layer as site of solubilization.In part from Doctor in Biology thesis of F. Pinio, University of Palermo, Italy.     

Excess volumes of the binary mixtures of trichloroethylene withn-alcohols at 30 and 40°C

Volumes of mixing binary systems formed by trichloroethylene with n-alcohols (1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, and 1-octanol) were measured as a function of composition at 30 and 40°C, by dilatometric measurements. All the systems show a change of sign for V ^E from negative to positive as the mole fraction trichloroethylene increases at both temperatures The positive value of the excess volumes increase as carbon chain length increases. The results are explained in terms of depolymerization of hydrogen bonded alcohol aggregates and weak hydrogen-bonding interaction of the type Cl-H–O between unlike molecules.