Coagulation rate measurements

Perikinetic Coagulation. If colloidal particles are of such dimensions that they are subject to thermal motion, the transport of these particles is accomplished by this Brownian motion. Collisions occur when one particle enters the sphere of influence of another particle. The coagulation rate measuring the decrease in the concentration of particles with time, N (in numbers/ml.), of a nearly monodisperse suspension corresponds under these conditions to the rate law for a second order reaction (15) ... 

Coagulation Rate Measurements. As shown by Matijevic and Ottewill (13), the turbidity T. resulting from the formation of the solid phase in a solution can be defined by the relation ... 

The sediment volume of silica in CCl solutions of poly (methyl methacrylate) was approximately 9 cc g-l but variable results were found in solutions of polystyrene, depending on the molecular wt. of the polymer. Lower M.W. samples are poor stabilizers and the dispersions are so unstable that optical coagulation rates could not be measured with confidence. Figure 5 shows the general trend in CCl. All polymers, whatever their composition, are superior to the pure solvent. 

Flocculation rate limitation. The adsorption step was rate limiting for the overall flocculation process in this system. Polymer adsorption rate measurements for dispersed systems reported in the literature (2,26) do not lend themselves to direct comparisons with the present work due to lack of information on shear rates, flocculation rates, and particle and polymer sizes. Gregory (12) proposed that the adsorption and coagulation halftimes, tA and t, respectively, should be good indications of whether or not the adsorption step is expected to be rate limiting. The halftimes, tA and t, are defined as the times required to halve the initial concentrations of polymer and particles, respectively. Adsorption should not limit the flocculation rate if... 

Summary plot of experimentally derived stability ratios, Wexp, of hematite suspensions, as a function of added electrolyte or adsorbate concentration at pH around 6.5 (pH = 10.5 for Ca2+ and Na+). Hematite concentration is about 10-20 mg/ . The stability ratio, Wexp, was determined from measurements on the coagulation rate it is the reciprocal of the experimentally determined collision efficiency factor, a. 

Figure 1. Measurement of perikineHc coagulation rate under various solution...

B) Relative colloid stability as a function of the total concentration of coagulant added, Ct, at constant pH—obtained from the measurement of perikinetic coagulation rates according to Equation 3. (Ludox LS = 0.3 gram/liter)... 

Rapid coagulation is, in fact, not quite as simple as this, because the last part of the approach of two particles is (a) slowed down because it is difficult for liquid to flow away from the narrow gap between the particles, and (b) accelerated by the van de Waals attraction between the particles. Lichtenbelt and co-workers205 have measured rapid coagulation rates by a stopped-flow method and found them, typically, to be about half the rate predicted according to equation (8.18). 

Coagulation rates have been measured as a function of electrolyte concentration for a number of sols96 196 204-206, and the predicted linear relationship between log W and log c in the slow-coagulation region seems to be well confirmed. In addition, the experimental values of d log W d log c, although somewhat variable, are of the right order of magnitude compared with theoretical slopes. 

Conceptually similar results were demonstrated by Krutzer et al. [14], who measured the orthokinetic coagulation rate under laminar Couette flow and isotropic turbulent flow (as well as other flow conditions). Despite equal particle collision rates, significance differences were observed in the overall rates indicating different collision efficiencies (higher collision efficiencies were found under a turbulent flow regime). Thus, identical chemical properties of a dispersion do not determine a single collision efficiency the collision efficiency is indeed dependent upon the physical transport occurring in the system. 

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