Aggregation, slow

Finally, after particles are aggregated, slow strengthening of bonds often occurs. Actually, most particle pairs are kept aggregated by a junction that involves a great number of separate bonds, and that number may increase with ageing. 

Fertility and productivity of soils usually increase with decrease in particle size and increase in surface area, at least up to the point where other factors may become controlling. These other factors that are so likely to interfere with plant growth in the soils of finest texture are poor aeration, unsatisfactory aggregation, slow water infiltration and poor drainage. 

Arsenate adsorption on ferrihydrite consisted of a period of rapid uptake followed by slow adsorption for at least 8 days 43). The rate of the slow adsorption reaction is considered to be limited by diffusion into the ferrihydrite aggregates. Slow adsorption kinetics similar to those for phosphate are expected for arsenate because of the similar chemistry of these two anions. Arsenate adsorption data adhere to the Elovich kinetic model indicating a diffusion limited reaction. Arsenate desorption rates were much slower than arsenate adsorption rates, also consistent with a diffusion limited process. A model was developed that assumes that 63% of adsorbing sites are located at the exteriors of aggregates and reach arsenate equilibrium rapidly, while 37% of adsorbing sites are located in the interiors of aggregates with access being diffusion limited. 

It follows from Example 6a that the time constant for Brownian aggregation is inversely proportional to the cube of the particle diameter. That means that the aggregation slows down as the particles grow. When they reach a certain size, the shear aggregation will take over. 

Other properties of association colloids that have been studied include calorimetric measurements of the heat of micelle formation (about 6 kcal/mol for a nonionic species, see Ref. 188) and the effect of high pressure (which decreases the aggregation number [189], but may raise the CMC [190]). Fast relaxation methods (rapid flow mixing, pressure-jump, temperature-jump) tend to reveal two relaxation times t and f2, the interpretation of which has been subject to much disagreement—see Ref. 191. A fast process of fi - 1 msec may represent the rate of addition to or dissociation from a micelle of individual monomer units, and a slow process of ti < 100 msec may represent the rate of total dissociation of a micelle (192 see also Refs. 193-195). 

The second case concerns situations where not all particle encounters result in aggregation. This is known as slow coagulation. This was addressed first by Fuchs [ ] again we follow [39, 57]. 

In slow coagulation, particles have to diffuse over an energy barrier (see the previous section) in order to aggregate. As a result, not all Brownian particle encounters result in aggregation. This is expressed using the stability ratio IV, defined as... 

Mixing. The most widely used mixing method is wet ball milling, which is a slow process, but it can be left unattended for the whole procedure. A ball mill is a barrel that rotates on its axis and is partially filled with a grinding medium (usually of ceramic material) in the form of spheres, cylinders, or rods. It mixes the raw oxides, eliminates aggregates, and can reduce the particle size. 

Oxidation—Reduction. Redox or oxidation—reduction reactions are often governed by the hard—soft base rule. For example, a metal in a low oxidation state (relatively soft) can be oxidized more easily if surrounded by hard ligands or a hard solvent. Metals tend toward hard-acid behavior on oxidation. Redox rates are often limited by substitution rates of the reactant so that direct electron transfer can occur (16). If substitution is very slow, an outer sphere or tunneling reaction may occur. One-electron transfers are normally favored over multielectron processes, especially when three or more species must aggregate prior to reaction. However, oxidative addition... 

As two particles approach in a liquid their charge fields may interact and form two minima as depicted in Figure 6.8. If the particles approach to a distance Li, known as the primary minimum they aggregate to form a configuration with minimum energy - and rapid coagulation is said to take place. On the other hand, if the particles remain separated at a distance L2, the secondary minimum, loose clusters form which do not touch. This is known as slow coagulation and is the more easily reversed. 

The phase separation process at late times t is usually governed by a law of the type R t) oc f, where R t) is the characteristic domain size at time t, and n an exponent which depends on the universality class of the model and on the conservation laws in the dynamics. At the presence of amphiphiles, however, the situation is somewhat complicated by the fact that the amphiphiles aggregate at the interfaces and reduce the interfacial tension during the coarsening process, i.e., the interfacial tension depends on the time. This leads to a pronounced slowing down at late times. In order to quantify this effect, Laradji et al. [217,222] have proposed the scaling ansatz... 

The most recent advance in treating HIV infections has been to simultaneously attack the virus on a second front using a protease inhibitor. Recall from Section 27.10 that proteases are enzymes that catalyze the hydrolysis of proteins at specific points. When HIV uses a cell s DNA to synthesize its own proteins, the initial product is a long polypeptide that contains several different proteins joined together. To be useful, the individual proteins must be separated from the aggregate by protease-catalyzed hydrolysis of peptide bonds. Protease inhibitors prevent this hydrolysis and, in combination with reverse transcriptase inhibitors, slow the reproduction of HIV. Dramatic reductions in the viral load in HIV-infected patients have been achieved with this approach. 

---