Journal of Colloid Science (J Colloid Sci )

Publisher: Elsevier


Discontinued in 1965. Continued as Journal of Colloid and Interface Science (0021-9797).

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Publications in this journal

  • [Show abstract] [Hide abstract]
    ABSTRACT: The effects produced by benzene or hexane as spreading solvents upon the surface pressure-area isotherms of octadecanol and stearic acid were investigated. Diluting the spreading solution resulted in an increase in the area/molecule at π = 1 dyne/cm. This expansion was greater with hexane than with benzene. Monolayers of stearic acid expanded more than those of octadecanol upon adding benzene liquid or vapor to the surface. Benzene vapor was irreversibly adsorbed on a monolayer of stearic acid. Octadecanol monolayers expanded when the concentration of benzene in the subphase was increased. An expansion of the monolayer with age was noted. This effect was greater for octadecanol than stearic acid monolayers. Aging could be attributed to changes in the structure of the monolayer as well as to contamination. Expansions resulting from both aging and solvent effects were greater at low surface pressures.A model based on the relative rates of solvent evaporation and diffusion into the subphase during the spreading process is proposed. The surface concentrations of benzene evaluated from experimental data and the model are compared. The two values agree within a factor of three.
    Journal of Colloid Science 04/2002; 15(2).
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    ABSTRACT: There are discussed two factors controlling the thickness h of a free film of liquid between two bubbles of radius R pressed against one another, the mechanical properties of the film and the temperature. The role of the viscosity, η, is analyzed on the basis of the formula (σ surface tension, u the receding velocity of the film perimeter), which is the simple consequence of the formula for the thickness of the film left behind the receding wetting perimeter (Derjaguin, 1943). A similar formula is also used for the analysis of the role of yield value of the film. The temperature does not change the thickness of the black free films (∼100A.) in contrast to the thicker films governed by electric repulsion. The jumpwise thinning of free films is studied by microfilming.The method of crossed polarized metal wires is described, which permits measurement of the potential barrier preventing metallic contact in liquid media. The measurements of this barrier in water solutions of electrolytes as a function of potential of the wires are interpreted on the basis of our theory of colloid stability. The existence of repulsive forces (disjoining pressure) at high electrolyte concentrations independent of the potential proves their nonelectrostatic origin. These measurements were also used to calculate Hamaker's constant of molecular attraction and to determine the potential of zero charge of some metals.
    Journal of Colloid Science 01/1993;
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    ABSTRACT: The separation of adsorption complexes formed by the interaction of sodium dodecyl sulfate (SDS) with gelatin at pH values below the isoelectric point has been investigated. Two pH conditions were employed. In one, the pH of the reaction mixture was adjusted to 4.1 after the component solutions had been mixed. In the other, the pH of each of the component solutions was adjusted to 4.1 before the solutions were mixed and the pH of the reaction mixtures was allowed to vary with the reaction. Concentration regions of complex solubility, complex precipitation, maximum gelatin precipitation, and complex solubilization characterized these reactions. Analyses of the supernatant solutions for both gelatin and SDS indicate that the adsorption is not exclusively continuous. Under the first pH condition, the reaction mechanism appears to be all-or-none in the region of complex precipitation forming a complex in which only one-half of the cationic sites are occupied, and predominantly statistical in the region of maximum gelatin precipitation, terminating in a complex in which all the cationic sites are occupied. Solubilization of the precipitated complex is achieved by the physical adsorption of additional SDS with the hydrophilic groups oriented toward the water. Under the second pH condition, an exclusively all-or-none mechanism appears to prevail in the regions of complex precipitation and solubilizations. The reactions result in the formation of an insoluble complex in which one-half the cationic groups on the gelatin are involved and a soluble complex in which all the cationic groups are involved.
    Journal of Colloid Science 01/1970; 20(2):177-186.
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    ABSTRACT: A mechanism is proposed for the ionic fluxes in excitable membranes based on recent studies of monolayer permeation and of interfacial ionic transport. The excitable membrane is assumed to be a homogeneous lipid bilayer with anionic groups on the inner and outer surfaces and nonselectively adsorbed cations at these sites. The bound ions are in high concentration at the membrane surface and they cause the enhanced ionic fluxes when released during activity. The free ions, which are in equilibrium with the adsorbed ions, give rise to the resting ionic fluxes. Starting with the steady state ionic concentration gradients, the current due to “depolarizing electrodes” causes the concentration of potassium ions near the outer surface to increase, and it is assumed that these ions exchange with and release the bound sodium ions. Because of the increased sodium concentration at the membrane surface, there is an increased sodium ion flux across the membrane. This flux causes a release and a reverse flux of potassium ions by a similar process. The fluxes have been calculated in terms of several membrane parameters, and they can account qualitatively for the ion fluxes and permeability ratios at rest and during activity, the actions of some ions and pharmacologic agents, the effects of ion depletion, etc. Therefore, the mechanism provides a basis for explaining the ionic events at excitable membranes in terms of physical processes at the membrane level.
    Journal of Colloid Science 01/1966;
  • Journal of Colloid Science 01/1966; 20(9):950-61.
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    ABSTRACT: In aqueous systems, fatty acid salts below their critical micelle concentration (CMC) diffuse through collodion membranes of graded porosity at a rate which varies indirectly as the chain length of the fatty acids and directly as the porosity of the membranes. For a given salt the rate is somewhat less than for a nonelectrolyte of the same molecular weight.When the concentration of the fatty acid salt is above the CMC, the rate is dependent on the size of the micelles relative to the pore size. Phospholipids, which exist in solution as very large micelles, are virtually impermeable even in very porous membranes. Cholesterol or benzene solubilized in lipid micelles can be transported through porous membranes, but the pores must be large enough to accommodate the micelles.
    Journal of Colloid Science 01/1966; 20(9):923-32.
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    ABSTRACT: The time course of swelling of a membrane during water imbibition is explained using time-independent properties of the membrane and an equation developed from physicochemical considerations. The corneal stroma is an example of a membrane for which sufficient experimental data are available to compare theory and experiment. When account is taken of the uncertainties in both theory and experimental data, there is good agreement between the predicted and observed time course of membrane swelling.
    Journal of Colloid Science 01/1966; 20(9):962-89.
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    ABSTRACT: A previously developed description of multi-process near-equilibrium systems in terms of individual kinetically independent processes is extended to some membrane processes. For the examples considered it is shown that this description is at least as convenient as the application of irreversible thermodynamics; for example, it leads to quite obvious criteria for “anomalous” osmosis. Moreover, irreversible thermodynamics does not properly describe systems in which solution leaks through the membrane. A by-product of the process description is that it aids in understanding equilibrium systems such as classical Donnan equilibria and the electromotive force of Donnan cells both with and without the separating membrane.
    Journal of Colloid Science 12/1965; 20(9):990-999.
  • Journal of Colloid Science 12/1965; 20(9):1034-1056.
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    ABSTRACT: In an earlier paper, monolayer permeability was derived on the basis of the fluctuations that occur in monolayer density at equilibrium. In this paper, the same model is used to derive the monolayer transport properties. First, expressions are developed for the probability and for the frequency of local expansions. These expressions are then used to derive the self-diffusion coefficient (D), the viscosity (η), and the thermal conductivity (κ) of a monolayer in terms of properties that are related to the surface isotherm. Whereas D has a reasonable magnitude, η is extremely small and many orders of magnitude lower than measured surface viscosities. The differences are discussed in terms of the monolayer model and the effect of the subphase. The utility of the model for processes involving natural membranes is also considered.
    Journal of Colloid Science 11/1965; 20(8):789-800.
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    ABSTRACT: The critical micelle concentrations (CMC) of long-chain cationic and anionic surfactants in water are lowered by the addition of ordinary salts like NaCl. This is usually ascribed to electrostatic effects. It has been found that the CMC of hexadecyltrimethylammonium bromide in water at 30°C. is at first decreased by the addition of the lower quaternary bromides and then increases markedly at higher salt concentration. The initial CMC decrease is in the order K+ < (CH3)4N+ < (C2H5)4N+ < (n − C3H7)4N < (n − C4H9)4N+. There is a continually decreasing value of the CMC in increasingly concentrated KBr solutions. However, there is a minimum CMC value for each added quaternary salt. Those for (CH3)4N+ and (C2H5)4N+ are found in approximately 0.09 M and 0.01 M salt, respectively, that for the n-propyl compound is at 10−3M solution. In more concentrated salt solutions the CMC is three to five times greater than in water, with the greatest increase found in (n − C4H9)4 NBr solution, and the smallest increase in (CH3)4NBr at equal concentrations. The results are interpreted in terms of the effects of added electrolytes on the hydrogen-bonded structure of water. It is concluded that micelle formation is rendered more difficult by electrolytes which organize the solvent structure, and occurs at lower soap concentrations in the presence of structure-disrupting electrolytes like the alkali halides.
    Journal of Colloid Science 10/1965; 20(7):732-41.
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    ABSTRACT: The mathematical relationships have been developed for describing the penetration of fluids into the void spaces of a collection of uniform solid spheres. The pressure required for initial penetration or “breakthrough” pressure is defined in terms of the porosity of the spherical model and the contact angle of the fluid. Calculated data, covering the porosity range of 47.64% to 25.95%, and contact angles of 90° to 180°, are presented. These relationships allow the determination of particle radius from standard mercury penetration and porosity data.
    Journal of Colloid Science 10/1965; 20(8):893-911.
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    ABSTRACT: Aqueous micelles of phosphatidic acid are prepared by ultrasonic radiation. In the pH range studied, ≧ 7, these dispersions consist of highly charged polyanions and have low turbidities. The interactions of buffered systems of phosphatidic acid with cations can be studied by turbidimetric titrations. At pH 7.2, increased turbidity occurs in 0.2 N LiCl or 0.4 N NaCl, however, KCl and tetramethylammonium chloride produce no change up to concentrations of 0.75 N. In 10−5M CaC12 the turbidity increases and rises steeply to 2 × 10−4M. Somewhat higher concentrations are necessary with MgCl2 . Additions of univalent cations to phosphatidic acid containing Ca reduces the turbidity by exchange with Ca.In systems containing sodium citrate, the concentrations of CaCl2 required to produce given turbidity changes are greater than in comparable systems containing NaCl. This gives a measure of the concentration of CaCit− formed. From the known formation constant of CaCit−, the Ca+2 concentration in equilibrium with the anions of citric and phosphatidic acids is calculated. This permits the evaluation of the formation constant of CaPA. Values obtained at pH 7.2, 8.8, and 9.6 are 1.2 × 104.
    Journal of Colloid Science 10/1965; 20(7):777-87.
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    ABSTRACT: A thermodynamic analysis of adsorption from a single-component fluid, either vapor or liquid, on the surface of a single-component solid is systematically developed. The analysis is based on the Gibbsian treatment of surface regions and assumes only that the interfaces are planar, that the solid and fluid phases are mutually insoluble, and that the solid is inert. The treatment is then applied to the interpretation of adhesional wetting (contact angle) and immersional wetting (heat of wetting) measurements. A relationship between the quantities obtained from these two types of wetting measurements is derived. This relationship is of the GibbsHelmholtz form and involves the dependence of the contact angle on temperature. Problems which arise in a proposed experimental test of the relationship are discussed.
    Journal of Colloid Science 10/1965; 20(8):801-821.
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    ABSTRACT: The relative surface acidity of several alumina powders with a variety of specific surface areas has been measured by a microcalorimetric technique. The alumina surfaces studied here are those for which the catalytic activity for alcohol dehydration has been measured. The technique used was to measure the heats of immersion (ΔHi) in pyridine and 2,6-dimethyl pyridine. A maximum in ΔHi for both liquids was observed as a function of a particle size corresponding to a maximum in the catalytic activity. The technique was also applied to NiSO4·xH2O samples, and the results were compared to other surface acidity measurements for these samples.
    Journal of Colloid Science 10/1965; 20(8):838–845.
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    ABSTRACT: Adsorption-desorption isotherms for water vapor and a high charge density sodium vermiculite were determined at 25°C. and at 50°C. X-ray patterns were obtained at various stages of hydration of the clay. Heats of immersion were determined calorimetrically for the dry clay and for partially hydrated samples. The adsorption of water appears to take place in two distinct steps corresponding with the intercalation of the lattice with one and with two monomolecular layers of water. The shape of the isotherms can be seen as the superposition of two Langmuir-type isotherms. The observed hysteresis is attributed to a retardation of the adsorption process owing to the development of elastic stresses in the crystallites during the initial peripheral penetration of water between the unit layers. On the assumption that the desorption isotherm represents equilibrium values, the thermodynamic constants for the sorption process were determined.The calorimetric data suggest that the integral heats of sorption per mole of water are constant during the formation of each layer of water, the heat of sorption for the first layer per mole of water being about twice that for the second layer. Agreement between the calorimetric data and the heats determined from the isotherms at two temperatures is reasonable for the first stage, and good for the second.The integral entropy of sorption is negative with respect to the entropy of liquid water. Since the system was treated as a one-component system (the adsorbate), the computed integral entropy includes entropy changes in the solid due to the parting of the unit layers and changes in the positions of the interlayer cations.From the isotherms the net work of unit layer interaction can be computed as a function of unit layer distance, from which the pressures required to squeeze out the water layers are derived. The net work consists of the hydration energy proper minus the potential energy of electrostatic and van der Waals unit layer attraction. From an estimate of the attraction energy, the hydration energy is estimated to be considerably smaller than ion hydration energy in bulk solution.
    Journal of Colloid Science 10/1965; 20(8):822–837.
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    ABSTRACT: The absolute angular scattered intensities for a Mie scattering system have been determined. A Dow polystyrene latex of large diameter (DEM = 1.305 μ) was studied with unpolarized, vertically polarized, and horizontally polarized incident light. The necessary expressions relating the geometrical, optical, and calibration constants of a Brice-Phoenix photometer with the quantities directly related to the Mie intensity functions were developed. Two features of the experimental technique were explored in detail: the use of polarized incident radiation and the effect of the solid angle subtended by the receiver aperture. Generally, excellent agreement between the theoretical Mie intensity functions and the corresponding experimental absolute intensities was obtained over the whole angular range.
    Journal of Colloid Science 10/1965; 20(8):875-892.
  • [Show abstract] [Hide abstract]
    ABSTRACT: Isotherms for the adsorption of nitrogen and argon on poly(methylmethacrylate) were obtained at three temperatures over a pressure range from a few microns to the saturated vapor pressure of the adsorbing gas. Differential and integral enthalpies and entropies were calculated and indicate a heterogeneous surface with adsorption energies higher than those observed for unsubstituted hydrocarbons. Clustering functions were calculated and indicate that the adsorption occurred in clusters throughout the range investigated.
    Journal of Colloid Science 10/1965; 20(8):846-856.
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    ABSTRACT: The interaction of nitrous oxide with real (oxide-coated) surfaces of both n- and p-type germanium has been investigated in the range of 10–300 torr and 200–400°C. The n-type samples promoted greater decomposition than the p-type samples. In all cases studied, not a trace of oxygen resulting from the decomposition could be detected in a mass spectrometer; obviously, the oxygen was incorporated in further oxide film formation. Pretreatment of germanium with oxygen decreased the extent of its interaction with nitrous oxide.Experiments with a 34% enriched 15N14N16O clearly showed that the decomposi tion mechanism primarily consists of the rupture of the NO bond to set a nitrogen molecule free.
    Journal of Colloid Science 10/1965; 20(8):857-866.
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    ABSTRACT: Measurements of the critical micelle concentration and of micellar molecular weight are reported for polyoxyethylene (23) lauryl alcohol in ethanol-water and dioxane-water solvent systems. With increasing concentration of additive, the c.m.c. increases and the micellar weight decreases; at concentrations above about 25%, no micelle formation occurs. The results are explained qualitatively in terms of the free energy requirements for micellization.
    Journal of Colloid Science 09/1965; 20(7):728-731.