Colloidal system determination

Food emulsions and foams are complex dispersions that constitute a major part of the food products that are consumed daily. The correct elaboration of such colloidal systems determines the functional properties of the final product such as texture or long-term stability. Accordingly, the optimization of the food product depends fundamentally on the comprehension of the structural characteristics of its components. Foams and emulsions are dispersions of air and liquid in another immiscible liquid, respectively. Formation of these dispersions is subject to the presence of amphiphilic molecules, which tend to place themselves at the air-water interface (foams) or the oil-water interface (emulsion). Thus, they constitute molecular barriers that stabilize the dispersion. The composition and structure of these molecular barriers determine ultimately the behavior of foams and emulsions. 

In order to achieve a true comparison between both catalytic systems, colloidal and molecular, which display very different reaction rates, a series of experiments were carried out with the homogeneous molecular system, decreasing the catalyst concentration in the studied allylic alkylation reaction. The reaction evolution is monitored taking samples at different reaction times and analysing each of them by NMR spectroscopy (to determine the conversion) and HPLC chromatography with chiral column (to determine the enantioselectivity of I and II). For molecular catalyst systems, the Pd/substrate ratio was varied between 1/100 and 1/10,000. For the latter ratio, the initial reaction rate was found comparable to that of the colloidal system (Figure 2a), but interestingly the conversion of the substrate is quasi complete after ca. 100 h in... 

The value of TK is best determined by warming a dilute solution of surfactant, and noting the temperature at which it becomes clear. Table 10.4 lists the Krafft points for a series of colloidal systems based on aqueous solutions of sodium alkyl sulphate (cf. structure III). 

In order to utilise our colloids as near hard spheres in terms of the thermodynamics we need to account for the presence of the medium and the species it contains. If the ions and molecules intervening between a pair of colloidal particles are small relative to the colloidal species we can treat the medium as a continuum. The role of the molecules and ions can be allowed for by the use of pair potentials between particles. These can be determined so as to include the role of the solution species as an energy of interaction with distance. The limit of the medium forms the boundary of the system and so determines its volume. We can consider the thermodynamic properties of the colloidal system as those in excess of the solvent. The pressure exerted by the colloidal species is now that in excess of the solvent, and is the osmotic pressure II of the colloid. These ideas form the basis of pseudo one-component thermodynamics. This allows us to calculate an elastic rheological property. Let us consider some important thermodynamic quantities for the system. We may apply the first law of thermodynamics to the system. The work done in an osmotic pressure and volume experiment on the colloidal system is related to the excess heat adsorbed d Q and the internal energy change d E ... 

Measurements of the chemical composition of an aqueous solution phase are interpreted commonly to provide experimental evidence for either adsorption or surface precipitation mechanisms in sorption processes. The conceptual aspects of these measurements vis-a-vis their usefulness in distinguishing adsorption from precipitation phenomena are reviewed critically. It is concluded that the inherently macroscopic, indirect nature of the data produced by such measurements limit their applicability to determine sorption mechanisms in a fundamental way. Surface spectroscopy (optical or magnetic resonance), although not a fully developed experimental technique for aqueous colloidal systems, appears to offer the best hope for a truly molecular-level probe of the interfacial region that can discriminate among the structures that arise there from diverse chemical conditions. 

The invention of the electron microscope in the 1930s by Knoll and Ruska cleared the way for scientists to take an even closer look at vesicles and other colloidal structures [5]. Improving the resolution of the optical microscope roughly by the factor that the optical microscope improved that of the unaided eye, the finer structures of colloidal systems became visible. With the electron microscope, single bilayers can be made visible and the distance between lamellae can be determined. Thus, the structure of a given system can be determined to up to 1/10000000 of a millimeter, which is about the distance of six atoms in a molecule. The most impressive results are obtained with the freeze fracture and cryo-TEM methods [6]. 

Mack (58, 59) points out that asphaltenes from different sources in the same petro-lenes give mixtures of approximately the same rheological type, but sols of the same asphaltenes in different petrolenes differ in flow behavior. Those in aromatic petrolenes show viscous behavior and presumably approach true solution. Those in paraffinic media show complex flow and are considered to be true colloidal systems. Pfeiffer and associates (91) consider that degree of peptization of asphaltene micelles determines the flow behavior. Thus, a low concentration of asphaltenes well peptized by aromatic petrolenes leads to purely viscous flow. High concentrations of asphaltenes and petrolenes of low aromatic content result in gel-type asphalts. All shades of flow behavior between these extremes are observed. 

The discussions above highlight the following (a) the structure of a dispersion is a complicated function of interaction forces (b) equilibrium thermodynamics dictates what is possible and what is not, but (c) for lyophobic colloids, ultimately it is kinetics that determines whether the structures predicted by thermodynamics can be realized in practice. One of the major objectives of thermodynamic and kinetic studies of colloidal systems is to be able to predict and... 

Occasionally, granular silica (supplied either by the Ottawa Silica Co. or Fisher Scientific Co.) was added to the plutonium solution for various periods before centrifugation to determine its effect on the colloidal system. The silica was first dry sieved, washed thoroughly, then oven dried at 120 °C. the particle sizes ranged from 280 to 390p. Other chemicals used were reagent grade. 

Particle asymmetry is a factor of considerable importance in determining the overall properties (especially those of a mechanical nature) of colloidal systems. Roughly speaking, colloidal particles can be classified according to shape as corpuscular, laminar or linear (see, for example, the electron micrographs in Figure 3.2). The exact shape may be complex but, to a first approximation, the particles can often be treated theoretically in terms of models which have relatively simple shapes (Figure 1.1). 

Colloidal systems are generally of a polydispersed nature - i.e. the molecules or particles in a particular sample vary in size. By virtue of their stepwise build-up, colloidal particle and polymer molecular sizes tend to have skew distributions, as illustrated in Figure 1.2, for which the Poisson distribution often offers a good approximation. Very often, detailed determination of relative molecular mass or particle size distribution is impracticable and less perfect experimental methods, which yield average values, must be accepted. The significance of the word average depends on the relative contributions of the various molecules or particles to the property of the system which is being measured. 

In many colloidal systems, the double layer is created by the adsorption of potential-determining ions for example, the potential 0o the surface of a /Silver iodide particle depends on the concentration of silver (and iodide) ions in solution. Addition of inert electrolyte increases k and results in a corresponding increase of surface charge density caused by the adsorption of sufficient potential-determining silver (or iodide) ions to keep 0O approximately constant. In contrast, however, the charge density at an ionogenic surface remains constant on addition of inert electrolyte (provided that the extent of ionisation is unaffected) and 0O decreases. 

The forces acting between two surfaces in contact or near - contact determine the behavior of a wide spectrum of physical properties. These can include friction, lubrication, the flow properties of particulate dispersions, and, in particular, the adsorption and adhesion phenomena, the stability of colloidal system [1,2] and the ability to form Langmuir monolayer at the air - water interface. 

As discussed in Chapters 1-7, diffusion, Brownian motion, sedimentation, electrophoresis, osmosis, rheology, mechanics, interfacial energetics, and optical and electrical properties are among the general physical properties and phenomena that are primarily important in colloidal systems [12,13,26,57,58], Chemical reactivity and adsorption often play important, if not dominant, roles. Any physical chemical feature may ultimately govern a specific industrial process and determine final product characteristics, and any colloidal dispersions involved may be deemed either desirable or undesirable based on their unique physical chemical properties. Chapters 9-16 will provide some examples. 

The potential in the diffuse layer decreases exponentially with the distance to zero (from the Stem plane). The potential changes are affected by the characteristics of the diffuse layer and particularly by the type and number of ions in the bulk solution. In many systems, the electrical double layer originates from the adsorption of potential-determining ions such as surface-active ions. The addition of an inert electrolyte decreases the thickness of the electrical double layer (i.e., compressing the double layer) and thus the potential decays to zero in a short distance. As the surface potential remains constant upon addition of an inert electrolyte, the zeta potential decreases. When two similarly charged particles approach each other, the two particles are repelled due to their electrostatic interactions. The increase in the electrolyte concentration in a bulk solution helps to lower this repulsive interaction. This principle is widely used to destabilize many colloidal systems. 

The properties of the colloidal systems are considerably influenced by factors such as polydispersity, and particle s size and shape. However, from the theoretical and experimental point of view, the methods of determining... 

The equilibrium state is determined by a minimization of the free energy. The total interaction in colloidal systems is mainly determined by electrostatic interactions and can be divided in three components. The first component occurs at interactions between net charged molecules or molecules with asymmetric charged distribution. These charge distributions can often be described by multipole expansions, i.e., a combination of monopole, dipole, quadrupole, etc., and is a fruitful approach if each multipole expansion can be described by one or two terms. The interaction is given by the sum of interactions between the terms, where the first contribution is the interaction between ions and is given by Coulomb s law and is the main contribution in systems with... 

Several methods have been developed for preparing nanoparticles and are optimized on the basis of their physicochemical properties (e.g., size and hy-drophilicity) with regard to their in vivo fate after parenteral administration. The selection of the appropriate method for preparing drug-loaded nanoparticles depends on the physicochemical properties of the polymer and the drug. On the other hand, the procedure and the formulation conditions will determine the inner structure of these polymeric colloidal systems. Two types of systems with different inner structures are possible ... 

Two main techniques have been used to determine the particle size distribution of colloidal systems PCS and electron microscopy including both SEM and TEM. The QELS technique for Brownian moment measurement, offers an accurate procedure for measuring the size distribution of nanoparticles. The PCS technique does not require any particular preparation for analysis and is excellent due to its efficiency and accuracy. However, its dependency on the Brownian movement of particles in a suspended medium may affect the particle size determination. 

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