Hquid interfaces

The rate-limiting step typically occurs at the air—Hquid interface and, for biological species without diffusion limitations, the overall relationship can be simply written at steady state as... 

The function of aeration in a wastewater treatment system is to maintain an aerobic condition. Water, upon exposure to air, tends to estabUsh an equihbrium concentration of dissolved oxygen (DO). Oxygen absorption is controlled by gas solubiUty and diffusion at the gas—hquid interface. Mechanical or artificial aeration may be utilised to speed up this process. Agitating the water, creating drops or a thin layer, or bubbling air through water speeds up absorption because each increases the surface area at the interface. 

The rate of mass transfer (qv) depends on the interfacial contact area and on the rate of mass transfer per unit interfacial area, ie, the mass flux. The mass flux very close to the Hquid—Hquid interface is determined by molecular diffusion in accordance with Pick s first law ... 

Interfacial Contact Area and Approach to Equilibrium. Experimental extraction cells such as the original Lewis stirred cell (52) are often operated with a flat Hquid—Hquid interface the area of which can easily be measured. In the single-drop apparatus, a regular sequence of drops of known diameter is released through the continuous phase (42). These units are useful for the direct calculation of the mass flux N and hence the mass-transfer coefficient for a given system. 

Interaction of Solids With Flotation Reagents. For flotation to occur with the aid of reagents, such compounds must adsorb at the sohd—hquid interface unless the soHd to be floated is naturally hydrophobic. In this latter case only depression can be attempted by the use of additional ions or depressants that hinder bubble—particle adhesion. Frothers (typically long-chain alcohols) and/or modifying agents such as hydrocarbon oils can, however, be used to enhance the collection of naturally hydrophobic soflds such as M0S2, talc, or plastics. 

AH corrosion inhibitors in use as of this writing are oil-soluble surfactants (qv) which consist of a hydrophobic hydrocarbon backbone and a hydrophilic functional group. Oil-soluble surfactant-type additives were first used in 1946 by the Sinclair Oil Co. (38). Most corrosion inhibitors are carboxyhc acids (qv), amines, or amine salts (39), depending on the types of water bottoms encountered in the whole distribution system. The wrong choice of inhibitors can lead to unwanted reactions. Eor instance, use of an acidic corrosion inhibitor when the water bottoms are caustic can result in the formation of insoluble salts that can plug filters in the distribution system or in customers vehicles. Because these additives form a strongly adsorbed impervious film at the metal Hquid interface, low Hquid concentrations are usually adequate. Concentrations typically range up to 5 ppm. In many situations, pipeline companies add their own corrosion inhibitors on top of that added by refiners. 

Dispersion is the process of wetting the surface of the metal, thereby penetrating the oil film. Surfactants can reduce the surface tension and interfacial tension of the cleaning solution at the metal—Hquid interface. As the cleaner undercuts and penetrates the oil, the cleaner breaks the oil into small droplets which then float to the surface. 

Figure 4c illustrates interfacial polymerisation encapsulation processes in which the reactant(s) that polymerise to form the capsule shell is transported exclusively from the continuous phase of the system to the dispersed phase—continuous phase interface where polymerisation occurs and a capsule shell is produced. This type of encapsulation process has been carried out at Hquid—Hquid and soHd—Hquid interfaces. An example of the Hquid—Hquid case is the spontaneous polymerisation reaction of cyanoacrylate monomers at the water—solvent interface formed by dispersing water in a continuous solvent phase (14). The poly(alkyl cyanoacrylate) produced by this spontaneous reaction encapsulates the dispersed water droplets. An example of the soHd—Hquid process is where a core material is dispersed in aqueous media that contains a water-immiscible surfactant along with a controUed amount of surfactant. A water-immiscible monomer that polymerises by free-radical polymerisation is added to the system and free-radical polymerisation localised at the core material—aqueous phase interface is initiated thereby generating a capsule sheU (15). 

Wo-tting Single. Pa.rticles. When a particle is submerged in a Hquid, the work of wetting a surface, n>, is the change in interfacial energy density times area, a, as the soHd—gas and Hquid—gas interfaces are replaced by a soHd—Hquid interface. 

Thus, the enthalpy and temperature of the vapor—Hquid interface are related to the Hquid temperature and gas enthalpy at any point in the column through a ratio of heat- and mass-transfer coefficients. 

When the void space in an agglomerate is completely filled with a Hquid (Fig. Ic), the capillary state of wetting is reached, and the tensile strength of the wet particle matrix arises from the pressure deficiency in the Hquid network owing to the concave Hquid interfaces at the agglomerate surface. This pressure deficiency can be calculated from the Laplace equation for chcular capillaries to yield, for Hquids which completely wet the particles ... 

An attraction also exists at the interface between a Hquid and an insoluble soHd. The interfacial tension is lower than the sum of the surface tensions of the two phases. Duprn s equation is appHcable to the soHd—Hquid interface and has the foUowing form ... 

Combination with equation 2 for energy of adhesion of a soHd—Hquid interface (eq. 3) gives equation 5 ... 

Zone refining is one of a class of techniques known as fractional solidification in which a separation is brought about by crystallization of a melt without solvent being added (see also Crystallization) (1 8). SoHd—Hquid phase equiUbria are utilized, but the phenomena are much more complex than in separation processes utilizing vapor—Hquid equiHbria. In most of the fractional-solidification techniques described in the article on crystallization, small separate crystals are formed rapidly in a relatively isothermal melt. In zone refining, on the other hand, a massive soHd is formed slowly and a sizable temperature gradient is imposed at the soHd—Hquid interface. 

Since the separation occurs at the soHd—Hquid interface, the purification rate is maximized by having many zones close together. If this is not possible and only one zone can be passed at a time, the rate is maximized by having the first zone as long as possible and decreasing the length of subsequent zones. 

When two reactants in a catalytic process have such different solubiUty properties that they can hardly both be present in a single Hquid phase, the reaction is confined to a Hquid—Hquid interface and is usually slow. However, the rate can be increased by orders of magnitude by appHcation of a phase-transfer catalyst (40,41), and these are used on a large scale in industrial processing (see Catalysts, phase-TRANSFEr). Phase-transfer catalysts function by faciHtating mass transport of reactants between the Hquid phases. Often most of the reaction takes place close to the interface. 

Adsorption of dispersants at the soHd—Hquid interface from solution is normally measured by changes in the concentration of the dispersant after adsorption has occurred, and plotted as an adsorption isotherm. A classification system of adsorption isotherms has been developed to identify the mechanisms that may be operating, such as monolayer vs multilayer adsorption, and chemisorption vs physical adsorption (8). For moderate to high mol wt polymeric dispersants, the low energy (equiUbrium) configurations of the adsorbed layer are typically about 3—30 nm thick. Normally, the adsorption is monolayer, since the thickness of the first layer significantly reduces attraction for a second layer, unless the polymer is very low mol wt or adsorbs by being nearly immiscible with the solvent. 

The molecules in a gas-hquid interface are in tension and tend to contract to a minimum surface area. This tension may be quantified by the surface tension, which is defined as the force in the plane of the surface per unit length. Jasper" has made a critical evaluation of experimental surface tension data for approximately 2200 pure chem-ic s. He correlates surface tension C (mN/m = dyn/cm) with temperature T (°C) over a specified temperature range as... 

Xi Mole-fraction solute in hquid at gas-hquid interface (kmol solute)/(kmol liquid) (Ibmol solute)/(lbmol hquid)... 

Mass-Transfer Principles Dilute Systems When material is transferred from one phase to another across an interface that separates the two, the resistance to mass transfer in each phase causes a concentration gradient in each, as shown in Fig. 5-26 for a gas-hquid interface. The concentrations of the diffusing material in the two phases immediately adjacent to the interface generally are unequal, even if expressed in the same units, but usually are assumed to be related to each other by the laws of thermodynamic equihbrium. Thus, it is assumed that the thermodynamic equilibrium is reached at the gas-liquid interface almost immediately when a gas and a hquid are brought into contact. 

For fast chemical reactions the reactant A is by definition completely consumed in the thin film near the hquid interface. Thus, x = 0, and... 

For extraction, the mixing usually takes place either in a vessel which also serves as the settler (these can be baffled or unbaffled), or a separate mixing compartment (usually baffled if there is a gas-hquid interface, and usually unbaffled if it is liquid filled). 

Coalescence The coalescence of droplets can occur whenever two or more droplets collide and remain in contact long enough for the continuous-phase film to become so thin that a hole develops and allows the liquid to become one body. A clean system with a high interfacial tension will generally coalesce quite rapidly. Particulates and polymeric films tend to accumulate at droplet surfaces and reduce the rate of coalescence. This can lead to the ouildup of a rag layer at the liquid-hquid interface in an extractor. Rapid drop breakup and rapid coalescence can significantly enhance the rate of mass transfer between phases. 

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