Experimental methods light scattering

These results permit the determination of molecular weights of r id-chain poly-iiKrs from experimental values of D and [tj] by using Eq. (11) and the values of Aq = 3.8 X 10 erg/deg which oirrespond to P = 5.11 and 4> = 2.862 x 10 ([t ] is measured in dl/g). The values of M calculated in this manner are reasonable and agree with the results obtained by direct methods (light scattering) ... 

The study of the concentration dependence / is a very informative and sensitive method for analyzing the molecular interactions in binary systems (Vuks, 1974). This dependence is obtained experimentally from light scattering data in solution or diffusion. Then, >ising / J xi), one can calculate the most important thermodynamic quantities of the system. 

This chapter is the narrowest in scope of any chapter in this book. In it we discuss a single experimental procedure and its interpretation. It is appropriate to examine light scattering in considerable detail, since the theory underlying this method is relatively unfamiliar to students and the interpretation yields information concerning a variety of polymer parameters. 

Until now we have looked at various aspects of light scattering under several limiting conditions, specifically, C2 = 0, 0 = 0, or both. Actual measurements, however, are made at finite values of both C2 and 6. In the next section we shall consider a method of treating experimental data that consolidates all of the various extrapolations into one graphical procedure. 

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. 

Normally (T is used without considering the solvent quality. However, a master low curve can only be established using such a method. In Table 5 a comparison of the model prediction with the experimental findings, obtained by laser light scattering measurements, is given. 

Viscosity, defined as the resistance of a liquid to flow under an applied stress, is not only a property of bulk liquids but of interfacial systems as well. The viscosity of an insoluble monolayer in a fluid-like state may be measured quantitatively by the viscous traction method (Manheimer and Schechter, 1970), wave-damping (Langmuir and Schaefer, 1937), dynamic light scattering (Sauer et al, 1988) or surface canal viscometry (Harkins and Kirkwood, 1938 Washburn and Wakeham, 1938). Of these, the last is the most sensitive and experimentally feasible, and allows for the determination of Newtonian versus non-Newtonian shear flow. 

An experimental method based on the theories for rainbow phenomena has been applied to the measurement of droplet size and velocity and to the detection of non-sphericity.[7] In this method, a comparison between two droplet diameters is deduced from two different optical interference patterns observed in a rainbow that is created by a droplet scattering laser light. Once a rainbow pattern is... 

Figure 4.1. Time scales for rotational motions of long DNAs that contribute to the relaxation of the optical anisotropy r(t). Experimental methods used to study these motions in different time ranges are also indicated along with the authors and dates of some early work in each case. FPA, Fluorescence polarization anisotropy (Refs. 15, 18-20, and 87) TPD, transient photodichroism (Refs. 28 and 62) TEB, transient electric birefringence (Refs. 26 and 27) DDLS, depolarized dynamic light scattering (Ref. 116) TED, transient electric dichroism (Refs. 25, 115, and 130) Microscopy, time-resolved fluorescent microscopy (Ref. 176).

The experimental techniques for the study of conformational branched properties in solution are the same as used for linear chains. These are, in particular, static and dynamic light scattering, small angle X-ray (SAXS) and small angle neutron (SANS) scattering methods, and common capillary viscometry. These methods are supported by osmotic pressure measurements and, nowadays extensively applied, size exclusion chromatography (SEC) in on-line combination with several detectors. These measurements result in a list of molecular parameters which are given in Table 1. 

Three experimental methods that are capable of determining dissociation constants with a precision of the order of tenths of 1% have been most commonly used. Each of these methods—the cell potential method (2), the conductance method (3), and the optical method (4)—provides data that can be treated approximately, assuming that the solutions obey Henry s law, or more exactly on the basis of the methods developed in Chapter 19. We will apply the more exact procedures. As the optical method can be used only if the acid and conjugate base show substantial differences in absorption of visible or ultraviolet light, or differences in raman scattering or with the use of indicators, we shall limit our discussion to the two electrical methods. 

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