Colloids suspensions

The reaction mechanism for these products is not clearly understood, but the introduction of organo-metallic compounds (barium or iron salts in colloidal suspension) has been shown to have a beneficiai action on the combustion of diesel fuel in engines and reduce smoke. However, these products cause deposits to form because they are used in relatively large proportions (on the order 0.6 to 0.8 weight %) to be effective. 

The statistical mechanical approach, density functional theory, allows description of the solid-liquid interface based on knowledge of the liquid properties [60, 61], This approach has been applied to the solid-liquid interface for hard spheres where experimental data on colloidal suspensions and theory [62] both indicate 0.6 this... 

There are a number of complications in the experimental measurement of the electrophoretic mobility of colloidal particles and its interpretation see Section V-6F. TTie experiment itself may involve a moving boundary type of apparatus, direct microscopic observation of the velocity of a particle in an applied field (the zeta-meter), or measurement of the conductivity of a colloidal suspension. 

The entropically driven disorder-order transition in hard-sphere fluids was originally discovered in computer simulations [58, 59]. The development of colloidal suspensions behaving as hard spheres (i.e., having negligible Hamaker constants, see Section VI-3) provided the means to experimentally verify the transition. Experimental data on the nucleation of hard-sphere colloidal crystals [60] allows one to extract the hard-sphere solid-liquid interfacial tension, 7 = 0.55 0.02k T/o, where a is the hard-sphere diameter [61]. This value agrees well with that found from density functional theory, 7 = 0.6 0.02k r/a 2 [21] (Section IX-2A). 

Ldwen H, Hansen J-P and Madden P A 1993 Nonlinear counterion screening in colloidal suspensions J. Chem. Phys. 98 3275-89... 

In practice, e.g., in nature or in fonnulated products, colloidal suspensions (also denoted sols or dispersions) tend to be complex systems, consisting of many components that are often not very well defined, in tenns of particle size for instance. Much progress has been made in the understanding of colloidal suspensions by studying well defined model systems, which allow for a quantitative modelling of their behaviour. Such systems will be discussed here. 

In addition to their practical importance, colloidal suspensions have received much attention from chemists and physicists alike. This is an interesting research area in its own right, and it is an important aspect of what is referred to as soft condensed matter physics. This contribution is written from such a perspective, and although a balanced account is aimed for, it is inevitably biased by the author s research interests. References to the original literature are included, but within the scope of this contribution only a fraction of the vast amount of literature on colloidal suspensions can be mentioned. 

The remainder of this contribution is organized as follows. In section C2.6.2, some well studied colloidal model systems are introduced. Methods for characterizing colloidal suspensions are presented in section C2.6.3. An essential starting point for understanding the behaviour of colloids is a description of the interactions between particles. Various factors contributing to these are discussed in section C2.6.4. Following on from this, theories of colloid stability and of the kinetics of aggregation are presented in section C2.6.5. Finally, section C2.6.6 is devoted to the phase behaviour of concentrated suspensions. 

After preparation, colloidal suspensions usually need to undergo purification procedures before detailed studies can be carried out. A common technique for charged particles (typically in aqueous suspension) is dialysis, to deal witli ionic impurities and small solutes. More extensive deionization can be achieved using ion exchange resins. 

Even when well defined model systems are used, colloids are ratlier complex, when compared witli pure molecular compounds, for instance. As a result, one often has to resort to a wide range of characterization teclmiques to obtain a sufficiently comprehensive description of a sample being studied. This section lists some of tire most common teclmiques used for studying colloidal suspensions. Some of tliese teclmiques are discussed in detail elsewhere in tliis volume and will only be mentioned in passing. A few teclmiques tliat are relevant more specifically for colloids are introduced very briefly here, and a few advanced teclmiques are highlighted. 

Altliough tire behaviour of colloidal suspensions does in general depend on temperature, a more important control parameter in practice tends to be tire particle concentration, often expressed as tire volume fraction ((). In fact, for hard- sphere suspensions tire phase behaviour is detennined by ( ) only. For spherical particles... 

In most colloidal suspensions tire particles have a tendency to sediment. At infinite dilution, spherical particles with a density difference Ap with tire solvent will move at tire Stokes velocity... 

In practice, sedimentation is an important property of colloidal suspensions. In fonnulated products, sedimentation tends to be a problem and some products are shipped in the fonn of weak gels, to prevent settling. On the other hand, in applications such as water clarification, a rapid sedimentation of impurities is desirable. 

Many properties of colloidal suspensions, such as their stability, rheology, and phase behaviour, are closely related to the interactions between the suspended particles. The background of the most important contributing factors to these interactions is discussed in this section. 

In the previous section, non-equilibrium behaviour was discussed, which is observed for particles with a deep minimum in the particle interactions at contact. In this final section, some examples of equilibrium phase behaviour in concentrated colloidal suspensions will be presented. Here we are concerned with purely repulsive particles (hard or soft spheres), or with particles with attractions of moderate strength and range (colloid-polymer and colloid-colloid mixtures). Although we shall focus mainly on equilibrium aspects, a few comments will be made about the associated kinetics as well [69, 70]. 

Klein R and D Aguanno B 1996 Scattering properties of colloidal suspensions Light Scattering, Principles and Development ed W Brown (Oxford Clarendon) pp 30-102... 

Behrens S H, Borkovec M and Schurtenberger P 1998 Aggregation in charge-stabilized colloidal suspensions revisited Langmuir 1951-4... 

Pusey P N 1991 Colloidal suspensions Liquids, Freezing and Giass Transition ed J P Hansen, D Levesque and J Zinn-Justin (Amsterdam Elsevier) pp 763-942... 

Sood A K 1991 Structural ordering in colloidal suspensions Soiid State Phys. 45 1-73... 

Monovoukas Y and Cast A P 1989 The experimental phase diagram of charged colloidal suspensions J. Colloid Interface Sol. 128 533-48... 

Samples that contain suspended matter are among the most difficult types from which to obtain accurate pH readings because of the so-called suspension effect, ie, the suspended particles produce abnormal Hquid-junction potentials at the reference electrode (16). This effect is especially noticeable with soil slurries, pastes, and other types of colloidal suspensions. In the case of a slurry that separates into two layers, pH differences of several units may result, depending on the placement of the electrodes in the layers. Internal consistency is achieved by pH measurement using carefully prescribed measurement protocols, as has been used in the determination of soil pH (17). 

Prussian Blue. Reaction of [Fe(CN)3] with an excess of aqueous h on(Ill) produces the finely divided, intensely blue precipitate Pmssian Blue [1403843-8] (tetrairon(Ill) tris(hexakiscyanoferrate)), Fe4[Fe(CN)3]. Pmssian Blue is identical to Turnbull s Blue, the name which originally was given to the material produced by reaction of [Fe(CN)3] with excess aqueous h on(Il). The soHd contains or has absorbed on its surface a large and variable number of water molecules, potassium ions (if present in the reaction), and h on(Ill) oxide. The h on(Il) centers are low spin and diamagnetic h on(Ill) centers are high spin. Variations of composition and properties result from variations in reaction conditions. Rapid precipitation in the presence of potassium ion affords a colloidal suspension of Pmssian Blue [25869-98-1] which has the approximate composition KFe[Fe(CN)3]. Pmssian Blue compounds are used as pigments in inks and paints and its formation on sensitized paper is utilized in the production of blueprints. 

Analytical Methods. The lack of stable niobium compounds resulting from a pronounced tendency for hydrolysis to colloidal suspensions of... 

D. H. Nappet, Polymeric Stabilisation of Colloidal Suspensions, Academic Press, London, 1983 Ref. 6, p. 169. 

Hydrolysis of solutions of Ti(IV) salts leads to precipitation of a hydrated titanium dioxide. The composition and properties of this product depend critically on the precipitation conditions, including the reactant concentration, temperature, pH, and choice of the salt (46—49). At room temperature, a voluminous and gelatinous precipitate forms. This has been referred to as orthotitanic acid [20338-08-3] and has been represented by the nominal formula Ti02 2H20 (Ti(OH). The gelatinous precipitate either redissolves or peptizes to a colloidal suspension ia dilute hydrochloric or nitric acids. If the suspension is boiled, or if precipitation is from hot solutions, a less-hydrated oxide forms. This has been referred to as metatitanic acid [12026-28-7] nominal formula Ti02 H2O (TiO(OH)2). The latter precipitate is more difficult to dissolve ia acid and is only soluble ia concentrated sulfuric acid or hydrofluoric acid. 

The behavior of colloidal suspensions is controlled by iaterparticle forces, the range of which rarely extends more than a particle diameter (see Colloids). Consequentiy suspensions tend to behave like viscous Hquids except at very high particle concentrations when the particles are forced iato close proximity. Because many coating solutions consist of complex mixtures of polymer and coUoidal material, a thorough characterization of the bulk rheology requires a number of different measurements. 

AEROSOL A colloidal suspension of liquid or solid particles dispersed in gas. 

Filtration operations are capable of handling suspensions of varying characteristics ranging from granular, incompressible, free-filtering materials to slime-like compositions, as well as finely divided colloidal suspensions in which the cakes are incompressible. These latter materials tend to contaminate or foul the filter medium. The interaction between the particles in suspension and the filter medium determines to a large extent the specific mechanisms responsible for filtration. 

Define a colloidal suspension and give some examples. 

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