Reginald Mills

Density, conductance, transference numbers, and diffusion measurements in concentrated solutions of nickel chloride at 25C

The Hittorf technique for measuring transference numbers has been modified to produce precise data in concentrated aqueous electrolyte solutions. Density, molar conductance, transference number, tracer-diffusion, and mutual diffusion data are reported for aqueous NiCl2 solutions up to 4M concentration at 25°C.

Velocity Cross Correlations in Binary Mixtures of Simple Fluids

AbstractThe velocity cross correlation integrals

Velocity correlations in aqueous electrolyte solutions from diffusion, conductance and transference data: Application to concentrated solutions of nickel chloride and magnesium chloride

D_{{\text{ab}}}^{\text{J}} = (N/3)\mathop \smallint \limits_{\text{o}}^\infty< {\text{v}}_{{\text{1a}}} ({\text{t}}) \cdot {\text{v}}_{{\text{2b}}} (0) > {\text{dt,}} {\text{a}} {\text{ = }} {\text{1,2;}} {\text{b}} {\text{ = }} {\text{1,2}}

Closed capillary method for the diffusion of biological macromolecules

can be estimated from the intradiffusion coefficients D1° and D2° at each mole fraction x1 of component 1 on the basis of the exact relations among the Onsager phenomenological coefficients together with an assumed equation relating the joint diffusion coefficients DabJ. The results from several such equations are compared with experimental data and with similar results derived by Hertz in a different way to represent the behavior of fab≡DabJxb in ideal reference systems. In some cases the agreement with experimental data for relatively ideal systems is even better than given by Hertzs results. For greater accuracy in predicting the DabJ from Dadg data one would need a prediction of the limiting value of DaaJ at xa=0 for a=1,2. Presently known theory does not give a basis for estimating this limit reliably.

A thermodynamic approximation for the estimation of velocity correlation coefficients in binary liquid mixtures

The distinct diffusion coefficient is a measure of the coupling of the diffusive motions of two particles. It is given as the integral over a velocity cross correlation rather than the velocity self correlation that determines the self-diffusion coefficient. A hydrodynamic approximation for the distinct diffusion coefficient is proposed and then tested by comparison with data for a wide range of non-ionic binary mixtures. The hydrodynamic approximation gives negative distinct diffusion coefficients and is in qualitative agreement with most of the data. In many cases, deviations from the model results can be explained in terms of interactions which are not accurately treated by the model.

Relations between intradiffusion and viscosity coefficients. Tests of the albright equation

Velocity cross-correlation coefficients have been calculated for aqueous solutions of NiCl2 and MgCl2 up to concentrations of 4M. Examination of the concentration-dependence of these coefficients show that it is very similar for the two salts. There is no evidence for any special structural characteristics in NiCl2 solutions. The velocity correlation technique is apparently not sensitive enough to detect the small amount of complexation that is thought to be present in NiCl2 solutions.

Tracer (self)-diffusion of potassium ion in NaCl−KCl−H2O mixtures at 25°C

The intradiffusion coefficients of Na+, Cl− ions and water and the tracerdiffusion coefficients of Ca2+ ion have been measured in the ternary system NaCl−MgCl2−H2O at 25°C. The intradiffusion coefficients of Mg2+ in this system have been estimated from the corresponding Ca2+ diffusion measurements. Viscosities were measured at the same solution concentrations as were used for the diffusion experiments. Intradiffusion and tracerdiffusion coefficients in a range of temperatures from 5 to 45°C are reported for standard sea-water which is a member of the above ternary set.

Velocity cross-correlation coefficients for the binary systems methanol-water and acetone-water at 278 K and 298 K

The closed capillary method for the determination of self-diffusion coefficients of trace species in liquids has been further developed for use with biological macromolecules. In this development, a new correction to permit its use with γ-emitting radioisotopes has been introduced. The improved method has been applied to the case of a human blood lipoprotein.