Ionic strength solutions

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... 

Variable di in Equation 8.2 is the ion size parameter. In practice, this value is determined by fitting the Debye-Huckel equation to experimental data. Variables A and B are functions of temperature, and I is the solution ionic strength. At 25 °C, given I in molal units and taking a, in A, the value of A is 0.5092, and B is 0.3283. 

Another arena for the application of stochastic frictional approaches is the influence of ionic atmosphere relaxation on the rates of reactions in electrolyte solutions [19], To gain perspective on this, we first recall the early and often quoted triumph of TST for the prediction of salt effects, in connection with Debye-Hiickel theory, for reaction rates In kTST varies linearly with the square root of the solution ionic strength I, with a sign depending on whether the charge distribution of the transition state is stabilized or destabilized by the ionic atmosphere compared to the reactants. 

Product solution ionic strength, I Decreases with increasing I (smaller effect for nonionic surfactants)... 

Fig. 21 Wet thickness of PAA H) as a function of the solution ionic strength (IS) at a pH = 4, b pH = 5.8, and c pH = 10. The symbols represent different grafting densities of PAA in chains/nm. (Reproduced with permission from [89])...

Na Polyacrylate Dose / g kg CaC03 Figure 6 Effect of Na polyacrylate dose on solution ionic strength... 

There are a number of assumptions made in the model that are questionable, and these are probably responsible for the discrepancy between the predicted and observed behaviour of the slurries. For example, the steric contribution has been calculated assuming that the adsorbed layer has a well-defined thickness. For adsorbed polymers this is unlikely to be the case, as the volume fraction profile of the polymer will decay gradually as a function of distance from the surface. Furthermore, it was assumed that the effective ionic strength in the adsorbed polymer layer is the same as in solution. However, this also is unlikely since one of the main components of the solution ionic strength is the polymer itself, and unadsorbed polymer will be excluded from the adsorbed layer. Finally, the connectivity of the charged groups on the polymer was not considered, so its contribution to ionic strength may have been overestimated. 

From the preceding discussion, the most obvious way to improve the performance of polyacrylate-dispersed calcium carbonate slurries is to reduce the solution ionic strength by reducing the amount of non-adsorbed polymer in solution. 

Fundamental studies of the effects of sodium polyacrylate have shown it to be an electrosteric dispersant, for which the steric component of interparticle repulsion is the dominant one at the typical dose rates used commercially. In such dispersions the main contributor to solution ionic strength is unadsorbed polyacrylate. As well as representing a waste of valuable dispersant polymer, this unadsorbed material also reduces the effectiveness of the adsorbed material as a steric dispersant by compressing the conformation of the adsorbed layer. 

In Eq. 30, Uioo and Fi are the activity in solution and the surface excess of the zth component, respectively. The activity is related to the concentration in solution Cioo and the activity coefficient / by Uioo =fCioo. The activity coefficient is a function of the solution ionic strength I [39]. The surface excess Fi includes the adsorption Fi in the Stern layer and the contribution, f lCiix) - Cioo] dx, from the diffuse part of the electrical double layer. The Boltzmann distribution gives Ci(x) = Cioo exp - Zj0(x), where z, is the ion valence and 0(x) is the dimensionless potential (measured from the Stern layer) obtained by dividing the actual potential, fix), by the thermal potential, k Tje = 25.7 mV at 25 °C). Similarly, the ionic activity in solution and at the Stern layer is inter-related as Uioo = af exp(z0s)> where tps is the scaled surface potential. Given that the sum of /jz, is equal to zero due to the electrical... 

For ionic solutions, ionic strength is an important parameter, affecting the quenching constant. The rate constant for bimolecular quenching collisions should be corrected to the limiting value k% according to Br nsted theory... 

Extrapolation of Kc to infinite dilution to give K is usually easy because the activity coefficients of most ionic substances vary in a regular manner with ionic strength and follow the Debye-Hiickel equation (Eq. 6-33) in very dilute solutions (ionic strength < 0.01). 

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