Determination of the partially specific volumes of polyelectrolytes via density measurements

Theory: Important information about the state of solubility of polymer solutions can be obtained from the partially specific volume, which is given via density measurements. Differences in the chemical constitution of polymer chains (e.g. copolymers) in the most of the cases lead to different partial volumina. This fact is used in the preparative ultracentrifugation for the determination of the molecular weight and molecular weight distribution as well as for analysing of structural units in copolymers for the detection of microgels. Under the influence of the centrifugal field, the macromolecules sediment to the place of their own density, if (1-0) = 0 - partially specific volume of the polymer [cm3 . g-1] 0 - density of the solvent [g.cm-3] The partially specific volume can be calculated by using the following equation:

= 0 + (1-0)cp The basic of the method is the natural oscillation of a liquid or a gas in a measuring cell. The oscillation time varies with regard to the density of sample. The oscillation time can be calculated as follows.: T = 2(dVc + Mc/K)1/2

d - density of the sample Vc - Volume of the sample Mc - mass of the cell

d = K/(42Vc)T3- Mc/ Vc The factor F can be determined, if the oscillation periods for standard substances are measured, which densities (da and dw) are available. F = K/(42Vc) = (da-dw)/(Ta2-Tw2)

For this reason, the density of an unknown sample can be determined by measuring its oscillation period T. D = (da - F)/(Ta2-T2)

Experimental part: Chemicals: solution of sodium polyacrylate in water (1%)- anionic polymer PAA, solution of poly(diallyldimethylammonium chloride) in water (1%)-cationic polymer PDADMAC, solution of poly(ethylene imine) (1%)-cationic branched polymer PEI Procedure: 1) Clean the cell with water and measure the water value! 2) Dilute the 1% PAA solution to obtain the following concentrations: 0.5%, 0.1% 0.05%, 0.01% Measure the density of all solutions (min. 3 times)! 3) Repeate this procedure for the PDADMAC and PEI solutions! Discussion: 1) Calculate the average density value for all measurements! 2) Plot these average values against the concentration of the polymer solution! 3) Determine the partially specific volumina of the three polymers and discuss the differences with regard to the structure of the polymer!