Conductivity light scattering

The establishment of hydrolysis equilibria is usually very fast, as long as the hydrolysis species are simple. Polynuclear complexes are often formed rather slowly. Many of these polynuclear hydroxo complexes are kinetic intermediates in the slow transition from free metal ions to solid precipitates and are tlius thermodynamically unstable. Some metal-ion solutions age, that is, tliey change their composition over periods of weeks because of slow structural transformations of the isopoly ions. Such nonequilibrium conditions can frequently be recognized if the properties of metal-ion solutions (electrode potentials, spectra, conductivity, light scattering, coagulation effects, sedimentation rates, etc.) depend on the history of the solution preparation. 

Frequently, light scattering experiments are not conducted under theta conditions. This may be because theta conditions are not known or because of the greater ease associated with conducting light scattering measurements in good solvents. Baumann [53] proposed an equation that is equivalent to the Burchard-Stockmayer-Fixman extrapolation procedure for intrinsic viscosity (see below)... 

The various physical methods in use at present involve measurements, respectively, of osmotic pressure, light scattering, sedimentation equilibrium, sedimentation velocity in conjunction with diffusion, or solution viscosity. All except the last mentioned are absolute methods. Each requires extrapolation to infinite dilution for rigorous fulfillment of the requirements of theory. These various physical methods depend basically on evaluation of the thermodynamic properties of the solution (i.e., the change in free energy due to the presence of polymer molecules) or of the kinetic behavior (i.e., frictional coefficient or viscosity increment), or of a combination of the two. Polymer solutions usually exhibit deviations from their limiting infinite dilution behavior at remarkably low concentrations. Hence one is obliged not only to conduct the experiments at low concentrations but also to extrapolate to infinite dilution from measurements made at the lowest experimentally feasible concentrations. 

The authors thank the U.S. Army Research Office for financial support of this research at TCU and SMU. The light scattering and the thermal analysis experiments were conducted, respectively, by Dr. G.L. Hagnauer (Army Materials Technology Laboratory, Watertown, MA) and Dr. J.J. Meister (SMU). 

The experimental determination of RBA, however, is difficult but some attempts have been made and these include direct observation, measurements of electrical conductivity, shrinkage energy, gas adsorption and light scattering. The linear elastic response of paper has been explained in terms of various micromechanical models which take into account both fibre and network properties, including RBA. An example of one which predicts the sheet modulus, Es is given below ... 

The greatest disadvantage of all detector systems such as, e.g. FID, UV, diode array detection (UV-DAD), FL, refractory index (RI), light scattering detector (LSD) or conductivity, applied in combination with GC, LC or CZE, is that they only provide an electric signal at the detector. The retention time alone of standard compounds, if available, is not sufficient for a reliable identification. LC separation of surfactant-containing extracts may often result in non-reproducible retention... 

---