Osmotic pressure concentration effect

The counterions form a diffuse cloud that shrouds each particle in order to maintain electrical neutrality of the system. When two particles are forced together their counterion clouds begin to overlap and increase the concentration of counterions in the gap between the particles. If both particles have the same charge, this gives rise to a repulsive potential due to the osmotic pressure of the counterions which is known as the electrical double layer (EDL) repulsion. If the particles are of opposite charge an EDL attraction will result. It is important to realize that EDL interactions are not simply determined by the Columbic interaction between the two charged spheres, but are due to the osmotic pressure (concentration) effects of the counterions in the gap between the particles. 

Abstract The fluxes of water and solutes across membranes are expressed as functions of differences of the hydraulic and osmotic pressures at both sides. Such difference equations are deduced from more fundamental differential equations. The distributions of concentration and pressure in a series array of membranes are derived. The order in which the individual membranes are placed exerts a strong influence upon the effects of the applied differences of hydraulic and osmotic pressures. The effect of the interchange of two membranes in a series array of an arbitrary number of membranes can be summarized in four simple rules. The special case of reversal of the flow is also discussed. 

A major difference of branched molecules from chain molecules is that more units are bound together and compressed into a very narrow space around the center of gravity. Hence, an immediate supposition is that in order for the monomer-monomer interaction to balance with the monomer-solvent interaction and the entropy force, and for the excluded volume effects to vanish, more attractive force between monomers are needed than is the case of chain molecules. Now we will focus our attention on concentrated systems such as non-solvent systems. An interesting idea is the influence of solvenf size on the osmotic pressure (screening effect) [19]. 

The effect of osmotic pressure in macromolecular ultraflltra-tlon has not been analyzed in detail although many similarities between this process and reverse osmosis may be drawn. An excellent review of reverse osmosis research has been given by Gill et al. (1971). It is generally found, however, that the simple linear osmotic pressure-concentration relationship used in reverse osmosis studies cannot be applied to ultrafiltration where the concentration dependency of macromolecular solutions is more complex. It is also reasonable to assume that variable viscosity effects may be more pronounced In macromolecular ultra-filtration as opposed to reverse osmosis. Similarly, because of the relatively low diffuslvlty of macromolecules conqiared to typical reverse osmosis solutes (by a factor of 100), concentration polarization effects are more severe in ultrafiltration. 

Theta conditions in dilute polymer solutions are similar to tire state of van der Waals gases near tire Boyle temperature. At this temperature, excluded-volume effects and van der Waals attraction compensate each other, so tliat tire second virial coefficient of tire expansion of tire pressure as a function of tire concentration vanishes. On dealing witli solutions, tire quantity of interest becomes tire osmotic pressure IT ratlier tlian tire pressure. Its virial expansion may be written as... 

Since capillary tubing is involved in osmotic experiments, there are several points pertaining to this feature that should be noted. First, tubes that are carefully matched in diameter should be used so that no correction for surface tension effects need be considered. Next it should be appreciated that an equilibrium osmotic pressure can develop in a capillary tube with a minimum flow of solvent, and therefore the measured value of II applies to the solution as prepared. The pressure, of course, is independent of the cross-sectional area of the liquid column, but if too much solvent transfer were involved, then the effects of dilution would also have to be considered. Now let us examine the practical units that are used to express the concentration of solutions in these experiments. 

These results show more clearly than Fq. (8.126)-of which they are special cases-the effect of charge and indifferent electrolyte concentration on the osmotic pressure of the solution. In terms of the determination of molecular weight of a polyelectrolyte by osmometry. ... 

When the superfluid component flows through a capillary connecting two reservoirs, the concentration of the superfluid component in the source reservoir decreases, and that in the receiving reservoir increases. When both reservoirs are thermally isolated, the temperature of the source reservoir increases and that of the receiving reservoir decreases. This behavior is consistent with the postulated relationship between superfluid component concentration and temperature. The converse effect, which maybe thought of as the osmotic pressure of the superfluid component, also exists. If a reservoir of helium II held at constant temperature is coimected by a fine capillary to another reservoir held at a higher temperature, the helium II flows from the cooler reservoir to the warmer one. A popular demonstration of this effect is the fountain experiment (55). 

The effect of osmotic pressure on yeast activity is of great importance, and is often overlooked. At salt concentrations up to 1.5%, the effect is slight salt concentrations of 2—2.5%, which are common in bread doughs, inhibit yeast activity considerably. Likewise, sugar concentrations above 4% produce apparent inhibition. Consequently, yeast-raised sweet doughs (15—20% sugar), contain very high yeast concentrations. 

Salt flux across a membrane is due to effects coupled to water transport, usually negligible, and diffusion across the membrane. Eq. (22-60) describes the basic diffusion equation for solute passage. It is independent of pressure, so as AP — AH 0, rejection 0. This important factor is due to the kinetic nature of the separation. Salt passage through the membrane is concentration dependent. Water passage is dependent on P — H. Therefore, when the membrane is operating near the osmotic pressure of the feed, the salt passage is not diluted by much permeate water. 

Osmotic Pinch Ejfect Feed is pumped into the membrane train, and as it flows through the membrane array, sensible pressure is lost due to fric tion effects. Simultaneously, as water permeates, leaving salts behind, osmotic pressure increases. There is no known practical alternative to having the lowest pressure and the highest salt concentration occur simultaneously at the exit of the train, the point where AP — AH is minimized. This point is known as the osmotic pinch, and it is the point backward from which hydrauhe design takes place. A corollary factor is that the permeate produced at the pinch is of the lowest quality anywhere in the array. Commonly, this permeate is below the required quahty, so the usual prac tice is to design around average-permeate quality, not incremental quahty. A I MPa overpressure at the pinch is preferred, but the minimum brine pressure tolerable is 1.1 times H. 

Molar masses can also be determined using other colligative properties. Osmotic pressure measurements are often used, particularly for solutes of high molar mass, where the concentration is likely to be quite low. The advantage of using osmotic pressure is that the effect is relatively large. Consider, for example, a 0.0010 M aqueous solution, for which... 

The effect of water salinity on crop growth is largely of osmotic nature. Osmotic pressure is related to the total salt concentration rather than the concentration of individual ionic elements. Salinity is commonly expressed as the electric conductivity of the irrigation water. Salt concentration can be determined by Total Dissolved Solids (TDS) or by Electrical Conductivity (EC). Under a water scarcity condition, salt tolerance of agricultural crops will be the primordial parameter when the quality of irrigation water is implicated for the integrated water resources management [10]. 

Id. Treatment of Data.—Typical osmotic data are shown in Figs. 38 and 39. Here the ratio ( n/c) of the osmotic pressure to the concentration is plotted against the concentration. If the solutions behaved ideally, van t Hoff s law Eq. (11) would apply and m/c should be independent of c. Owing to the large effective size of the polymer molecules in solution (Fig. 34) and the interactions between them which consequently set in at low concentrations, /c increases with c with a... 

The total mobile ion concentration (c++c ) inside the gel at equilibrium will inevitably exceed that in the external solution, c+ +c = vcj where v = v +v-. This must result in an osmotic pressure difference which tends to drive solvent into the gel from the less concentrated external solution. (We neglect for the moment the osmotic effects of polymer itself.) The osmotic pressure arising from the difference in mobile ion concentrations will be given approximately (see Appendix B), assuming the solutions to be dilute, by... 

But for any arbitrary polymer concentration C2 there will be another osmotic pressure due to the previously considered polymer-solvent interaction and to the associated elastic reaction of the network. Recalling the general relationship tz= — (mi —mi)/vi, we may calculate oTo from Eq. (38). At equilibrium the total osmotic pressure arising from the effects of all solutes must be zero, i.e., — JCq. Hence from Eqs. 

Van t Hoff introduced the correction factor i for electrolyte solutions the measured quantity (e.g. the osmotic pressure, Jt) must be divided by this factor to obtain agreement with the theory of dilute solutions of nonelectrolytes (jt/i = RTc). For the dilute solutions of some electrolytes (now called strong), this factor approaches small integers. Thus, for a dilute sodium chloride solution with concentration c, an osmotic pressure of 2RTc was always measured, which could readily be explained by the fact that the solution, in fact, actually contains twice the number of species corresponding to concentration c calculated in the usual manner from the weighed amount of substance dissolved in the solution. Small deviations from integral numbers were attributed to experimental errors (they are now attributed to the effect of the activity coefficient). 

The rheological properties of a fluid interface may be characterized by four parameters surface shear viscosity and elasticity, and surface dilational viscosity and elasticity. When polymer monolayers are present at such interfaces, viscoelastic behavior has been observed (1,2), but theoretical progress has been slow. The adsorption of amphiphilic polymers at the interface in liquid emulsions stabilizes the particles mainly through osmotic pressure developed upon close approach. This has become known as steric stabilization (3,4.5). In this paper, the dynamic behavior of amphiphilic, hydrophobically modified hydroxyethyl celluloses (HM-HEC), was studied. In previous studies HM-HEC s were found to greatly reduce liquid/liquid interfacial tensions even at very low polymer concentrations, and were extremely effective emulsifiers for organic liquids in water (6). 

The dissolution of a solute into a solvent perturbs the colligative properties of the solvent, affecting the freezing point, boiling point, vapor pressure, and osmotic pressure. The dissolution of solutes into a volatile solvent system will affect the vapor pressure of that solvent, and an ideal solution is one for which the degree of vapor pressure change is proportional to the concentration of solute. It was established by Raoult in 1888 that the effect on vapor pressure would be proportional to the mole fraction of solute, and independent of temperature. This behavior is illustrated in Fig. 10A, where individual vapor pressure curves are... 

Further development of the Flory-Huggins method in direction of taking into account the effects of far interaction, swelling of polymeric ball in good solvents [4, 5], difference of free volumes of polymer and solvent [6, 7] leaded to complication of expression for virial coefficient A and to growth of number of parameters needed for its numerical estimation, but weakly reflected on the possibility of equation (1) to describe the osmotic pressure of polymeric solutions in a wide range of concentrations. 

V, is the molar volume of polymer or solvent, as appropriate, and the concentration is in mass per unit volume. It can be seen from Equation (2.42) that the interaction term changes with the square of the polymer concentration but more importantly for our discussion is the implications of the value of x- When x = 0.5 we are left with the van t Hoff expression which describes the osmotic pressure of an ideal polymer solution. A sol vent/temperature condition that yields this result is known as the 0-condition. For example, the 0-temperature for poly(styrene) in cyclohexane is 311.5 K. At this temperature, the poly(styrene) molecule is at its closest to a random coil configuration because its conformation is unperturbed by specific solvent effects. If x is greater than 0.5 we have a poor solvent for our polymer and the coil will collapse. At x values less than 0.5 we have the polymer in a good solvent and the conformation will be expanded in order to pack as many solvent molecules around each chain segment as possible. A 0-condition is often used when determining the molecular weight of a polymer by measurement of the concentration dependence of viscosity, for example, but solution polymers are invariably used in better than 0-conditions. 

The thermodynamic approach does not make explicit the effects of concentration at the membrane. A good deal of the analysis of concentration polarisation given for ultrafiltration also applies to reverse osmosis. The control of the boundary layer is just as important. The main effects of concentration polarisation in this case are, however, a reduced value of solvent permeation rate as a result of an increased osmotic pressure at the membrane surface given in equation 8.37, and a decrease in solute rejection given in equation 8.38. In many applications it is usual to pretreat feeds in order to remove colloidal material before reverse osmosis. The components which must then be retained by reverse osmosis have higher diffusion coefficients than those encountered in ultrafiltration. Hence, the polarisation modulus given in equation 8.14 is lower, and the concentration of solutes at the membrane seldom results in the formation of a gel. For the case of turbulent flow the Dittus-Boelter correlation may be used, as was the case for ultrafiltration giving a polarisation modulus of ... 

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