Method for measuring the 2nd virial coefficient

Abstract

A method is described to determine the 2 virial coefficient of an ensemble of molecules dissolved in a selected solvent. Two distinct classes are described: monodisperse and polydisperse molecules. If the molecules are monodisperse, they must be prepared for a chromatographic separation and suitable columns selected. Following standard chromatographic separation procedures such as exemplified by the method of size exclusion chromatography, the sample passes through the separation columns, a multiangle light scattering detector, and a concentration detector. The effect of the columns is to produce a concentration profile of said sample that appears as a peak as it passes through the light scattering and concentration detectors. For each elution interval, &ngr; , a corresponding concentration value c and set of excess Rayleigh ratios R (&thgr; ) is measured for each scattering angle &thgr; . The excess Rayleigh ratios are extrapolated to &thgr;=0° resulting in the calculation of a single extrapolated value for each elution slice, viz., R (0°). Three sums are calculated from the data collected: 1) the sum of all c values over the measured concentration peak; 2) the sum of all (c ) values over the same concentration peak; and 3) the sum of all the extrapolated Rayleigh ratios over the measured light scattering peak. The 2 virial coefficient may be calculated directly from these three quantities once the molecule's molar mass is known. The same procedure is followed for polydisperse samples, however, the column set is replaced by a dilution means that does not fractionate the sample.