Filling solutions ionic strength

CE determination of pKa is new, compared to the other techniques [144—147]. It has the advantage of being a rather universal method since different detection systems can be coupled to CE. Because it is a separation technique, sample impurities seldom are a problem. A fused-silica capillary, with an inner diameter of 50-75 pm and 27-70 cm in length is filled with a dilute aqueous buffer solution (ionic strength... 

When a constant ionic strength of the test solution is maintained and the reference electrode liquid bridge is filled with a solution of a salt whose cation and anion have similar mobilities (for example solutions of KCl, KNO3 and NH4NO3), the liquid-junction potential is reasonably constant (cf. p. 24-5). However, problems may be encountered in measurements on suspensions (for example in blood or in soil extracts). The potential difference measured in the suspension may be very different from that obtained in the supernatant or in the filtrate. This phenomenon is called the suspension (Pallmann) effect [110] The appearance of the Pallmann effect depends on the position of the reference electrode, but not on that of ISE [65] (i.e. there is a difference between the potentials obtained with the reference electrode in the suspension and in the supernatant). This effect has not been satisfactorily explained it may be caused by the formation of an anomalous liquid-junction or Donnan potential. It... 

Capillary electrophoresis separation is performed in a flexible fused silica capillary tube that is filled with an appropriate buffer solution of defined pH and ionic strength (aqueous/nonaqueous). A small volume of sample (lower than 3-4% of the column volume) is needed to achieve efficient separation. This volume is introduced hydrodynamically (or less often electrokinetically) into the capillary to which an electrical potential is applied (Figure 13.7). Charged species of the sample exhibit... 

It is appropriate at this point to discuss the "apparent" pH, which results from the sad fact that electrodes do not truly measure hydrogen ion activity. Influences such as the surface chemistry of the glass electrode and liquid junction potential between the reference electrode filling solution and seawater contribute to this complexity (see for example Bates, 1973). Also, commonly used NBS buffer standards have a much lower ionic strength than seawater, which further complicates the problem. One way in which this last problem has been attacked is to make up buffered artificial seawater solutions and very carefully determine the relation between measurements and actual hydrogen ion activities or concentrations. The most widely accepted approach is based on the work of Hansson (1973). pH values measured in seawater on his scale are generally close to 0.15 pH units lower than those based on NBS standards. These two different pH scales also demand their own sets of apparent constants. It is now clear that for very precise work in seawater the Hansson approach is best. 

The ionic strength of the filling solution should be at least tenfold that of the sample so that the bridge solution will largely determine the junction potential and swamp out the effect of the sample ions. 

Electrophoresis — Movement of charged particles (e.g., ions, colloidal particles, dispersions of suspended solid particles, emulsions of suspended immiscible liquid droplets) in an electric field. The speed depends on the size of the particle, as well as the -> viscosity, -> dielectric permittivity, and the -> ionic strength of the solution, and it is directly proportional to the applied electric field. In analytical as well as in synthetic chemistry electrophoresis has been employed to separate species based on different speeds attained in an experimental setup. In a typical setup the sample is put onto a mobile phase (dilute electrolyte solution) filled, e.g., into a capillary or soaked into a paper strip. At the ends of the strip connectors to an electrical power supply (providing voltages up to several hundred volts) are placed. Depending on their polarity and mobility the charged particles move to one of the electrodes, according to the attained speed they are sorted and separated. (See also - Tiselius, - electrophoretic effect, - zetapotential). 

Fig. 12. The time-dependent uptake of liase by /3-lactoglobulin at ionic strength 0.15 at 25°C, as measured with a pH-stat. The initial point of each curve (filled circles) represents a measurement on a separate solution, with a flow apparatus capable of determining pH within 1 sec of mixing (Nozaki and Bunville, 1959).

Figxirc 8. Effect of pH on the optimum precipitation of protein by CMC from single component and binary solutions at 0.02 M ionic strength. Filled symbols indicate the binary mixture of lysozyme and ovalbumin. 

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