Reverse osmosis separations of polyethylene glycols in dilute aqueous solutions using porous cellulose acetate membranes

Reverse osmosis separations of eight polyethylene glycol (PEG) solutes in the average molecular weight range of 200 to 6750 in single-solute dilute aqueous solutions have been studied using porous cellulose acetate membranes at the operating pressures of 50, 75, and 100 psig. Diffusivity data for the above PEG solutes have also been obtained from experimental data on intrinsic viscosities. From an analysis of all experimental data, numerical values for the parameters representing the polar (?ΔΔG/RT), steric (δ^*ΣE_s), and nonpolar (ω^*Σs^*) forces governing reverse osmosis separations of PEG solutes have been generated. These numerical values are useful for precise characterization of cellulose acetate membranes for whose specifications sodium chloride is not the appropriate reference solute because of its low or practically negligible separation under reverse osmosis operating conditions. This work also illustrates that solute separation in reverse osmosis can predictably increase or decrease with increase in operating pressure depending on experimental conditions.     

Physicochemical criteria for reverse osmosis separation of monohydric and polyhydric alcohols in aqueous solutions using porous cellulose acetate membranes

Reverse osmosis data using different samples of Loeb-Sourirajan-type porous cellulose acetate membranes and single-solute aqueous solution systems involving 16 monohydric alcohols, 4 phenols, 18 polyhydric alcohols, pyrogallol, ethylene glycol monoethyl ether, 6 aldehydes, and 8 carbohydrates (sugars) have been studied. The solute concentrations used were in the range of 0.0005 to 0.003 g mole/l. (～100 ppm), and operating pressure used was 250 psig in all cases. The results show that correlations of acidity and basicity parameters (obtained from IR spectra) with solute separation data are equivalent, and they have predictive capability. A method is given for estimating Taft numbers (Σσ^*) for monohydric and polyhydric alcohols from available data based on the additive nature of σ^*. Data on solute transport parameters (D_AM/Kδ) for the different solutes were calculated from membrane performance data. For all the alcohols studied, the Σσ^*-versus-log (D_AM/K)δ correlation was found to be a straight line with a slope different for different ranges of Σσ^*, but independent of the porous structure of the membrane. Based on this result, it is shown that the parameters of the Taft equation can serve as a basis for expressing solute transport parameter, and this basis offers a means for predicting membrane performance for all alcohol–water systems from a single set of experimental data for a reference solute system. This prediction technique is illustrated using experimental data for 1,3-butanediol taken as the reference solute. The general applicability of the technique has been tested for predicting the separation of some aldehydes and carbohydrates.     

Reverse osmosis separation of hydrocarbons in aqueous solutions using porous cellulose acetate membranes

A physicochemical parameter, represented by the symbol Σs^*, based on molar solubility in water and molar attraction constants of Small, has been developed to express quantitatively the relative hydrophobicity, or nonpolar character, of the hydrocarbon molecule. The value of Σs^* can be calculated for a hydrocarbon from its chemical structure. The scale of Σs^* is consistent within each group of aromatic, cyclic, and noncyclic hydrocarbons. Reverse osmosis data have been obtained at 250 psig for single-solute aqueous feed solution systems involving low concentrations of 39 different hydrocarbons (including 13 aromatics, 10 cyclic, and 16 noncyclic compounds) and several samples of cellulose acetate membranes of different surface porosities. The effect of operating pressure on membrane performance has also been studied for two aromatic hydrocarbon solutes. The values of Σs^* for the solutes used were in the range of 425 to 924 for aromatic hydrocarbons, 521 to 931 for cyclic hydrocarbons, and 369 to 960 for noncyclic hydrocarbons. The reverse osmosis data have been correlated with Σs^* for each group of hydrocarbons studied. In all cases, positive solute separations were obtained, and the ratio [PR]/[PWP] was less than 1. With respect to each film, solute separation increased with increase in Σs^*, and decreased with increase in operating pressure. Also, solute separation decreased in the order aromatic hydrocarbon > cyclic hydrocarbon > noncyclic hydrocarbon at any given value of Σs^*. At a given operating pressure, for low values of Σs^* (～500 or less) solute separation increased with progressive decrease in average pore size on the membrane surface. For high values of Σs^* (～800 or more), solute separation initially increased with decrease in average pore size, then passed through a maximum and minimum with further decrease in average pore size, and again increased with still further decrease in average pore size. The results are discussed on the basis of preferential sorption of solute at the membrane–solution interface under the experimental conditions studied.     

Reverse osmosis separation of single and mixed alcohols in aqueous solutions using porous cellulose acetate membranes

Reverse osmosis transport for alcohol-water systems in the Taft number (σ^*) region of 0 to ?0.3 is explored in detail. The numerical value of the polar functional constant for alcohols is 15.5 for the above σ^* region in the operating pressure range of 50 to 500 psig for the cellulose acetate membrane material used. An analysis of the combined effect of operating pressure and mass transfer coefficient on the high-pressure side of the membrane shows that, under certain conditions, solute separation could pass through a maximum with increase in operating pressure. A general experession for solute separation is derived as a function of pore structure on membrane surface, polarity of solute, and operating conditions of the experiment. Alcohols behave independently in mixed solute systems. A method is described and illustrated for predicting alcohol separation in alcohol–sucrose–water feed solutions from data on single solute systems.     

Reverse osmosis separation of organic acids in aqueous solutions using porous cellulose acetate membranes

Reverse osmosis data obtained using porous cellulose acetate membranes and aqueous feed solutions involving one of 22 monocarboxylic acids, seven dicarboxylic acids, and four hydroxycarboxylic acids have been analyzed. The operating pressure used was 250 psig in all cases, and the solute concentration used was ～100 ppm in most cases. The results yield the following physicochemical criteria for preferential sorption at the membrane–solution interface with respect to the un-ionized acid. At pK_a = 4.2 (for monocarboxylic acids), or Taft number (σ^*) = 0.6 or Hammett number (σ) = 0, neither the un-ionized acid nor water is preferentially sorbed at the membrane–solution interface; at pK_a < 4.2 (for monocarboxylic acids) or σ^* > 0.6 or σ > 0, the un-ionized acid is preferentially sorbed at the membrane–solution interface. For practical purposes, preferential sorption of water at the membrane–solution interface may be considered negligible in the σ^* region of 0 to 0.6. The results also show that the criterion of acidity of the molecule governing the extent of its repulsion or attraction at the membrane–solution interface is valid for both ionized and un-ionized acid. Further, when the acid molecule contains three or more straight-chain carbon atoms not associated with a ? COOH group, the nonpolar character of the molecule also affects its separation in reverse osmosis.     

Polar and steric effects in reverse osmosis

The effects of polar parameter Σσ^* and steric parameter ΣE_s on reverse osmosis separations of alcohols, aldehydes, ketones, and ethers (noncyclic) in aqueous solutions involving single solute systems and porous cellulose acetate membranes are discussed. The least-squares and multiple-regression analyses of solute transport parameter data show that the separation of aldehydes, just as that of alcohols, is predominantly a function of Σσ^*, and that of ethers is predominantly a function of ΣE_s, whereas that of ketones is best represented as a function of both Σσ^* and ΣE_s. The results also indicate that even where water is preferentially sorbed at the membrane solution interface, solute separation in reverse osmosis is affected by the nonpolar character of the solute molecule. A general expression for solute transport parameter in reverse osmosis is presented for further study.     

Parameters for prediction of reverse osmosis performance of cellulose acetate propionate membranes

Data on reverse osmosis separations have been obtained for 12 alkali metal halide solutes and 24 organic solutes (including eight alcohols, four aldehydes, seven ketones, and five ethers) with cellulose acetate propionate (CAP) membranes using single-solute dilute aqueous feed solutions at 250 psig. From the analysis of these data, the parameters and correlations needed to calculate the values of solute transport parameter D_AM/Kδ for the above classes of inorganic and organic solutes for a CAP membrane of any surface porosity from data on D_AM/Kδ for NaCl only have been generated. These parameters and correlations enable one to predict reverse osmosis separations of different solutes included in the classes of compounds studied in this work, from a single set of experimental data on membrane specifications given in terms of pure water permeability constant and D_AM/Kδ for NaCl. The reverse osmosis characteristics of CAP material lie intermediate between those of cellulose acetate and aromatic polyamide materials reported in the literature.     

Reverse osmosis separation of phenols in aqueous solutions using porous cellulose acetate membranes

Reverse osmosis separations of phenol (9.4 to 108 ppm), p-cresol (108 ppm), and p-chlorophenol (129 ppm) were studied using Loeb-Sourirajan-type porous cellulose acetate membranes, and single-solute aqueous feed solutions at 500 psig and the indicated solute concentrations. It was found that, by dissociating the solute by changing the pH of the feed solution, all the above phenols could be separated by reverse osmosis. Solute separation increased with increase in the degree of dissociation of the solute in the feed solution; and, by the appropriate choice of pore size on the membrane surface, separations of phenol approaching the degree of dissociation of phenol in the feed solution could be obtained under the operating conditions used. Similar experiments using aniline (93 ppm) as the solute showed that dissociation of solute molecules in the feed solution could be a technique generally applicable for the reverse osmosis separation of nonionic solutes in aqueous solution. The effects of operating pressure in the range 250 to 1500 psig and pore size on the membrane surface on the separation of un-ionized phenol and p-chlorophenol showed that, with respect to single-solute aqueous feed solutions of phenols, the component whose relative acidity was greater was preferentially sorbed at the cellulose acetate membrane—aqueous solution interface, and the solute concentration in the membrane-permeated product solution was a function of the extent and mobility of each of the sorbed species.     

Correlation of the solubility of volatile liquids in molten polymers

The solubility of volatile liquids at infinite dilution (i.e., in the Henry's law region) in poly(vinyl acetate) (PVAc) and polystyrene (PS) at elevated temperatures has been correlated by plotting ln(1/K_p) against (T_c/T)², where T_c is the critical temperature of the solute and K_p is Henry's constant at temperature T and a total pressure of approximately at 1 atm, defined as P₁ = K_pV₁⁰, where P₁ is the partial pressure of the solute in the vapor phase and V₁⁰ is the solubility (cm³ solute per g polymer at 273.2 K and 1 atm). For this correlation, we have used experimental data available in the literature for 16 solutes covering 81 data points for PVAc and 17 solutes covering 82 data points for PS. We have calculated values of 1/K_p from the literature data reported in terms of the retention volume V_g⁰, weight-fraction Henry's constant H₁, and activity coefficient at infinite dilution Ω₁^∞. We have made the following observations: (1) for PVAc, ln(1/K_p) = ?1.564 + B(T_c/T)²; and (2) for PS, ln(1/K_p) = ?2.028 + B(T_c/T)². In both cases, we found that values of B, the slope in the ln(1/K_p) versus (T_c/T)² plots, vary with the acentric factor ω of the solutes. It has been found that, in both PVAc and PS at the same value of ω, values of B for slightly polar aromatic solutes are larger than those for nonpolar aliphatic solutes. Further, in PS at the same value of ω, values of B are smaller for strongly polar solutes than for slightly polar solutes, whereas in PVAc the opposite trend holds. This observation may be interpreted as that the solubility of strongly polar solutes in a polar polymer (e.g., PVAc) is greater than that of slightly polar and nonpolar solutes, whereas the solubility of strongly polar solutes in a nonpolar polymer (e.g., PS) is less than that of slightly polar solutes but greater than that of nonpolar solutes. The dependence of B on ω, observed in this investigation, is at variance with the correlations reported by Tseng, Lloyd, and Ward for PVAc and by Stiel and Harnish for PS.     

Activity of substrates in the catalyzed nucleation of poly(ethylene terephthalate) melts

The activity, Φ of AgBr, AgI, PbF₂, Ag₂S, LiF, and CaF₂ in the catalyzed nucleation of poly(ethylene terephthalate) (PET) melts was determined using a nonisothermal differential scanning calorimetry (DSC) technique. A comparison with existing experimental data was made. It is established that the higher the melting temperature of the substrate the lower its activity as a crystallization core in the heterogeneous nucleation of PET. The lateral surface energy, σ, the end surface energy, σ_e, the adhesion energy, β, and the difference between the surface energies at the substrate/melt, σ_sf, substrate/deposit, σ^*, and the total energy of misfit dislocations, E_d [i.e., σ_sf - (σ^* - E_d)] were calculated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 349–353, 1997     

Some transport characteristics of aromatic polyamide membranes in reverse osmosis

The effects of solute concentration in the range of 0.0013 to 1.051 molality in the feed solution and operating pressure in the range of 100 to 900 psig on solute transport parameter D_AM/Kδ in reverse osmosis have been studied for a class of laboratory-made aromatic polyamide membranes and aqueous sodium chloride feed solutions. The results showed that D_AM/Kδ for NaCl increased both with increase in operating pressure and solute concentration in the concentrated boundary solution on the high-pressure side of the membrane. A general expression for D_AM/Kδ for NaCl including the effects of both the above operating variables is given. These results are different from the corresponding results obtained for cellulose acetate membranes.     

Selection of Surfactants for Micellar-Enhanced Ultrafiltration

Abstract

The selection of a surfactant is an important issue in designing separations processes based on micellar-enhanced ultrafiltration. The binding of hydrophillic solutes to both ionic and nonionic micelles is considered and shown to be a function of the molecular structure of the surfactants, the concentration of the surfactant, and the electrolyte composition of the water. It is also shown that the passage of micelles is only partly restricted by polycarbonate membranes with 100 Å ports but is effectively restricted by some cellulose acetate membranes. Swelling the micelles by cosolubilizing certain nonpolar compounds was found to only marginally improve the separation efficiency. There appears to be an optimum surfactant molecular structure, but it will not be possible even under the best conditions to completely remove a hydrophilic solute such as phenol in a single stage. Thus, the process will necessarily be multistage.     

Copolymerization of styrene. IV. Copolymerization with esters of benzylidenecyanoacetic acid

Styrene was copolymerized in bulk with a number of esters of benzylidenecyanoacetic acid. The kinetic scheme of all pairs fitted the improved scheme of copolymerization, taking into account the effect of the penultimate unit. The Alfrey-Price Q and e values were calculated. Using the modified Taft equation, log (1/r₁) = ρ^*σ^* + δE_s, it was found that the relative reactivities of the ester monomers toward the polystyryl radical were correlated by the polar substituent constants σ^* of the ester alkyl groups (ρ^* = 0.14) and not by their steric substituent constants E_s (δ = 0.008).     

The Softness Parameters of Ions. Prediction of the Occurrence of Miscibility Gaps in Molten Salt Mixtures

Softness parameters σ_M for cations and σ_X for anions, have been calculated as dimensionless quantities for approx. 90 cations and 18 anions. They are given by σ_M = [σ_A (M^m+) - σ_A(H⁺)]/σ_A(H⁺) and σ_X = [σ_B(X^a?) - σ_B(OH^?)]/σ_A(H⁺) where σ_A = [σI_i(M) + ΔH⁰_h(M^m+)]/m and σ_B = [-E_a(X) + ΔH⁰_h(X^a?)]/a are Ahrland's parameters. The new normalized and comparative (to the test ions H⁺ and OH^?) softness parameters are positive for soft ions and negative for hard ones. These parameters, obtained independently, are used with a four-coefficient equation to calculate coordinate bond energies for metal halides with acceptable accuracy. Considerations of the average coordination in reciprocal molten salt mixture lead to an expression for the metathesis energy change as proportional to the product of the differences in softness parameters of the two cations and the two anions. An empirical one-coefficient equation involving the softness parameters is proposed to deal with next-nearest-neighbor interactions in binary common-ion molten salt mixtures. These relationships are then used with Blander and Topol's equation to predict the occurrence of irascibility gaps in uni-univalent reciprocal salt mixtures. The gaps found in other systems are also discussed in terms of the softness of the constituent ions.     

Reverse osmosis separations of aldehydes,ketones, and ethers in aqueous solutions using porous cellulose acetate membranes

Reverse osmosis data for a number of aldehyde, ketone, and ether solutes whose polar parameters Σσ* lie in the ranges of ?0.2 to 0.6, ?0.4 to 0.6, and ?0.49 to 0.6, respectively, have been analyzed. The results show that solute transport parameters can be expressed as a function of steric parameters ΣE_s only for ethers, polar parameter Σσ* only for aldehydes, and both ΣE_s and Σσ* for ketones. The numerical values of the functional proportionality constants ρ* and δ* associated with Σσ* and ΣE_s respectively, for the above class of solutes have been determined for operating pressures up to 500 psig, and a method of predicting solute separation from data on any reference solute only in each class has been established. The data on solute transport parameters for ethers, aldehydes, and ketones have been correlated with the corresponding data for sodium chloride through appropriate link constants. Analysis of data on mixed solute systems involving aldehydes and ketones show that the solutes behave independently in reverse osmosis.     

Structural and functional properties of sol-gel synthesized and microwave heated Pb0.8 Co0.2-zLazTiO3 (z = 0.05–0.2) nanoparticles

The present work reports the effect of La-substitution on structural and functional properties of lead cobalt titanate (PCT) perovskite structure as a function of variation of Co-content. The sol-gel synthesized and microwave heated Pb_0.8 Co_0.2-zLa_zTiO₃ (z?=?0.05, 0.1, 0.15 & 0.2) (PCLT) nanoparticles showed the presence of complete cubic phases while few were noted to be tetragonal lead titanate (PT) phases. The surface morphology was examined by field emission scanning electron microscope (FESEM) and high resolution transmission electron microscope (HRTEM). The HRTEM revealed fibers like nanoparticles at z?=?0.15 and 0.2. The Fourier transform infrared spectra attributed the presence of metal oxide bonds. Furthermore, the wide optical band gap energy (E_op) was acquired to be changing from 2.32 to 3.20?eV. In addition, the electrical parameters such as dielectric constant (ε'), dielectric loss (ε"), ac & dc-electrical conductivity (σ_ac & σ_dc), complex dielectric modulus (M^*) and complex impedance (Z^*) were studied as a function of frequency (f) and composition. Using power law fitting, the σ_dc values were determined. The z?=?0.15 content exhibited high σ_dc of ~ 2.51?×?10^?7 S/cm among all compositions. Besides, the results expressed the existence of short range and long range hopping conduction regions in dielectric modulus spectra. The Nyquist plots were drawn to elucidate the electrical conduction and relaxation mechanism. Later on, ferroelectric hysteresis loops were recorded for z?=?0.05–0.2.     

Dielectric relaxation behavior of conducting carbon black reinforced ethylene acrylic elastomer vulcanizates

The dielectric relaxation characteristics of conductive carbon black (CCB) reinforced ethylene acrylic elastomer (AEM) vulcanizates have been studied as a function of frequency (10¹–10⁶ Hz) at different filler loading over a wide range of temperatures (30–120°C). The effect of filler loadings on the dielectric permittivity (ε′), loss tangent (tan δ), complex impedance (Z*), and electrical conductivity (σ_ac) were studied. The variation of ε′ with filler loading has been explained based on the interfacial polarization of the fillers within a heterogeneous system. The effect of filler loading on the imaginary (Z″) and real (Z′) part of Z* were distinctly visible, which may be due to the relaxation dynamics of polymer chains at the polymer–filler interface. The frequency dependency of σ_ac has been investigated using percolation theory. The phenomenon of percolation in the composites has been discussed in terms of σ_ac. The percolation threshold (?_crit) occurred in the range of 20–30 phr (parts per hundred) of filler loading. The effect of temperature on tan δ, ε′, σ_ac, and Nyquist plots of CCB‐based AEM vulcanizates has been investigated. The CCB was uniformly dispersed within the AEM matrix as studied from the transmission electron microscope (TEM) photomicrographs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Imidocarbocyanines—spectral sensitizers of photographic silver halide emulsions

The review deals with the main results of several investigations of the relationship between the chemical structure of imidocarbocyanines and their basicity, redox potentials and photographic action in silver halide emulsions. A number of quantitative and qualitative relationships connecting p K_a and E_1,2^Ox(Rcd) of imidocarbocyanines and the Hammett σ_p-constants of different electronic substituents ranging from CH₃O (σ_p = ?0·27) to CF₃SO₂ (σ_p = 0·96) and the Taft σ^*-constants of groupings attached to the nitrogen atom (alkyl, aryl, ω-trifluoromethylalkyl or sulphoalkyl), are discussed. The main factors contributing to the total effect of spectral sensitization of silver halide emulsions by imidocarbocyanines are analyzed and a relationship between the degree of suppression of their sensitizing action by colour components and the tendency to aggregate on the surface of silver halide crystals is established.     

Permeability of phenol through cellulose acetate membranes by reverse osmosis in various alcoholic systems

Reverse osmosis separation of phenol in various alcoholic solutions using porous cellulose acetate membranes was investigated. The permeation behavior of phenol was measured for cellulose acetate membranes having various pore size distributions which were prepared by annealing at four different temperatures. Some differences were found between the aqueous and the alcoholic solutions in solute permeabilities and product rates. Membranes annealed at 90°C showed higher permselectivity than membranes annealed at lower temperatures. The pore character was classified into two types according to the relation of the product rate of 1-propanol and that of water. It was found in a series of alcoholic solutions that the permeability of phenol, the product rate, and the apparent partition coefficient are closely related to the carbon number of the alcohols, but the values of J_v × η (ca. 1.25 × 10^?4 poise·m³/m²·day) and of the permselectivity coefficient (ca. 0.83) remain constant. The result was analyzed by using the three-dimensional solubility parameter to obtain some information for the partition mechanism of solutes in aqueous and alcoholic solutions.     

Selective Adsorption of Solutes Based on Hydrogen Bonding

Abstract

Current evidence suggests that adsorption of solutes from a nonpolar solvent onto a polycarboxylic ester sorbent involves the formation of a hydrogen bond. This bond appears to be formed between a hydrogen atom of the solute and the carbonyl group of the sorbent. From studies involving single solutes it was observed that the primary amine aniline adsorbed nearly twice as much as the secondary amine N-methylaniline. The tertiary amine N,N-dimethylaniline, which does not contain a nitrogen-bonded hydrogen atom, was unable to bind to the sorbent. In studies involving mixtures, solutes were observed to be selectively adsorbed based on their hydrogen bonding abilities. A simple thermodynamic model which was developed to explain this adsorption was capable of accurately predicting separation factors for the selective adsorption of solutes from solute mixtures.