Rapidly Converging Activity Expansions For Representing The Thermodynamic Properties Of Fluid Systems: Gases, Non-Electrolyte Solutions, Weak And Strong Electrolyte Solutions

For dilute gases and non-electrolyte solutions in the McMillan–Mayer standard state, an activity expansion due to Mayer has great advantages over the normal concentration expansion (virial equation) for strongly associating species. For weakly interacting systems, both approaches are suitable. The activity expansion eliminates the need to differentiate between strong “chemical” interactions and weak “physical” interactions since the same equation is used in each situation. The equation has been modified to represent electrolyte solutions in the McMillan–Mayer standard state by requiring that it be consistent with the Debye–Hückel and higher order limiting laws for strong electrolytes and that it be equivalent to a chemical association model for weak electrolytes. The result is a compact equation which contains no arbitrary ion-size parameters and which does not require the classification of an electrolyte as strong or weak. For 2:2 electrolytes, the equation gives a very good fit to the anomalous low concentration region. For practical thermodynamic calculations, similar equations for molal activity coefficients are proposed; good fits of the data are obtained

Freezing Points Of Aqueous Alcohols: Free Energy Of Interaction Of The CHOH, CH₂, CONH And C[double bond]C Functional Groups In Dilute Aqueous Solutions

The freezing temperatures of dilute aqueous solutions of methanol, ethanol, 2-propanol, butanol, t-butanol, cyclohexanol and ethylene glycol were measured over the concentration range 0.1 to 1 mol kg–1. Osmotic coefficients at 0°C were calculated. The limiting pairwise interaction coefficients of the alcohols, plus a variety of polyhydroxy compounds and carbohydrates, were calculated at 25°C from the available data and then correlated using the additivity principle of Savage and Wood. This correlation approximates effective free energies of CH2 and CHOH group interactions with themselves and with each other. Literature data were used to estimate interactions between CONH and C[double bond]C groups. The CONH—CONH interaction appears to be large, consistent with a strong stabilizing effect of these on native protein structures. The CH2…CH2 interaction also indicates attractive forces between these groups. The present model for the hydrophobic interaction is most appropriate for small molecular interactions whereas previous treatments are best for situations involving site binding. The CHOH…CHOH and CH2…CONH interactions are small, while the CHOH…CH2 free energy of interaction is positive, due either to volume exclusion or net repulsive forces. The entropy change associated with the CH2…CH2 interaction is large and positive as expected and is not completely compensated by a corresponding enthalpy change. The entropy change associated with the CONH…CONH interaction indicates that few degrees of freedom are involved, which is consistent with the formation of a strong hydrogen bond. The correlation can be used to estimate thermodynamic properties of dilute non-electrolyte solutions and can also predict the effect of solutes on the solubility of solids and gases

Infrared Spectroscopy of Symbiotic Stars. VIII. Orbits for Three S-Type Systems: AE Arae, Y Coronae Australis, and SS 73-147

With new infrared radial velocities we have computed orbits of the M giants in three southern S-type symbiotic systems. AE Ara and SS 73-147 have circular orbits with periods of 803 and 820 days, respectively. The eccentric orbit of Y CrA has a period that is about twice as long, 1619 days. Except for CH Cyg it is currently the S-type symbiotic system with the longest period for which a spectroscopic orbit has been determined. The Paschen δ emission line velocities of AE Ara are nearly in antiphase with the M giant absorption feature velocities and result in a mass ratio of 2.7. Emission lines in the 1.005 μm region for the other two symbiotic systems are not good proxies for the hot components in those systems. There is no evidence that these three symbiotics are eclipsing. With spectral classes of M5.5 or M6, the three giants presumably also have velocity variations that result from pulsations, but we have been unable to identify specific pulsation periods in the absorption line velocity residuals

Infrared spectroscopy of symbiotic stars. IX. d-type symbiotic novae

Time-series spectra of the near-infrared 1.6 μm region have been obtained for five of the six known D-type symbiotic novae. The spectra map the pulsation kinematics of the Mira component in the Mira-white dwarf binary system and provide the center-of-ma

Infrared spectroscopy of symbiotic stars. X. Orbits for three S-type systems: V1044 Centauri, Hen 3-1213, and SS 73-96

Employing new infrared radial velocities, we have computed orbits of the cool giants in three southern S-type symbiotic systems. The orbit for V1044 Cen, an M5.5 giant, has a period of 985 days and a modest eccentricity of 0.16. Hen 3-1213 is a K4 giant, yellow symbiotic with an orbital period of 533 days and a similar eccentricity of 0.18. For the M2 giant SS 73-96 the orbital period is 828 days, and this system has a somewhat larger eccentricity of 0.26. Measurement of the H i Paschen δ emission lines, which may at least partially reflect the motion of the secondary in SS 73-96, results in a mass ratio of 2.4 for the M giant relative to the presumed white dwarf. The estimated orbital inclinations of V1044 Cen and Hen 3-1213 are low, about 40°. However, for SS 73-96 the predicted inclination is 90°, and so an ephemeris for eclipses of the secondary or the hot nebula surrounding it is provided. A search of the orbital velocity residuals of V1044 Cen and SS 73-96 for pulsation periods produced no realistic or convincing period for either star

Infrared Spectroscopy of Symbiotic Stars. X. Orbits for Three S-Type Systems: V1044 Centauri, Hen 3-1213, And SS 73-96

Employing new infrared radial velocities, we have computed orbits of the cool giants in three southern S-type symbiotic systems. The orbit for V1044 Cen, an M5.5 giant, has a period of 985 days and a modest eccentricity of 0.16. Hen 3-1213 is a K4 giant, yellow symbiotic with an orbital period of 533 days and a similar eccentricity of 0.18. For the M2 giant SS 73-96 the orbital period is 828 days, and this system has a somewhat larger eccentricity of 0.26. Measurement of the H i Paschen δ emission lines, which may at least partially reflect the motion of the secondary in SS 73-96, results in a mass ratio of 2.4 for the M giant relative to the presumed white dwarf. The estimated orbital inclinations of V1044 Cen and Hen 3-1213 are low, about 40°. However, for SS 73-96 the predicted inclination is 90°, and so an ephemeris for eclipses of the secondary or the hot nebula surrounding it is provided. A search of the orbital velocity residuals of V1044 Cen and SS 73-96 for pulsation periods produced no realistic or convincing period for either star