Size separation mechanism hydrodynamic chromatography

Hydrodynamic chromatography was originally described by Small (7) in 1974. A number of publications have appeared since then which describe the separation mechanism and sample detection methods used with HDC (5, 8-18). In addition, Van Gilder, et. al. (19) used HDC as the primary particle sizing technique in research on the particle size versus viscosity relationship of high solids paper coating latices. 

Size exclusion chromatography is the premier polymer characterization method for determining molar mass distributions. In SEC, the separation mechanism is based on molecular hydrodynamic volume. For homopolymers, condensation polymers and strictly alternating copolymers, there is a correspondence between elution volume and molar mass. Thus, chemically similar polymer standards of known molar mass can be used for calibration. However, for SEC of random and block copolymers and branched polymers, no simple correspondence exists between elution volume and molar mass because of the possible compositional heterogeneity of these materials. As a result, molar mass calibration with polymer standards can introduce a considerable amount of error. To address this problem, selective detection techniques have to be combined with SEC separation. 

One of these proposed a non-equilibrium process in which the separation was controlled by differing rates of diffusion for different molecular masses [23]. Other workers have proposed a separation by flow mechanism [24, 25] in which the larger molecules are excluded from the surface of the gel particles and remain in the centre of the solvent channels and are thus eluted first. The original theory did not invoke a porous structure for the gel, but this was modified later. The mechanism bears resemblance to that proposed for hydrodynamic chromatography (see Chapter 10). A further model suggested that the pore size distribution of the gel was directly responsible for its ability to separate molecules by size, and that there is a one-to-one correspondence with size of pores and size of molecules [26]. All these theories have been critically reviewed in the book by Yau et al [6]. 

Hydrodynamic chromatography. This technique is related to SEC in that it attempts to separate species according to their size, but several orders of magnitude larger than those encountered in solution chromatography. The mechanisms involved in hydrodynamic chromatography are different to SEC, but the basic experimental system is similar pump, injector, column and detector. Special columns and data analysis software are required, and the detectors usually employed are a differential refractometer, ultraviolet photometer or LALLS. Chapter 10 is devoted to this technique and full details can be found there. 

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