The correlation of excess molar refraction and excess volume for some binary solutions; a new approach

Continuous-dilution differential refractometry at useful precision Isotope effects on polarizability in liquids. A new method to determine excess volumes. Application to (water + deuterium oxide), (acetone + d6- acetone), and atT= 298.15 K and λ = (470, 520, 559 and 650) nm

“…data can be deconvoluted to yield differences in molar refractions for the liquids being compared, and excess molar refractions for their mixtures. Following earlier procedures, (1,2,8) the excess molar refractions have been interpreted in terms of the excess volumes of the mixture, and differences in the second moment and closure energies of the two components. Because c.d.d.r.…”

“…A c.d.d.r. experiment mixing 13 with( ex /R ( and V ex /V for the pseudo-binary system (8) and demonstrates that this kind of measurement is a highly sensitive and convenient probe for small non-idealities. For convenience, we refer to the method as c.d.d.r.…”

“…To a good approximation, to be refined later, the Lorenz-Lorentz function, LL(n) = {(n 2 − 1)/(n 2 + 2)}, is expected to scale linearly for ideally mixed solutions: (8) …”

“…In working up the data, it is convenient to employ a double difference formalism, dDR = DR soln − DR ideal = (xDR°+ R ex ) = R ex . Following Urbanczyk and Van Hook, (8) we define R ( = {(n 2 − 1)/(n 2 + 2)}V id , so that:…”

“…However, deviations from additivity are significant, and this has prevented application of the method. In the preceding paper, (8) we developed a method to evaluate corrections for non-additivity of molar refractions. This has opened the way to application of the c.d.d.r.…”