MASS TRANSPORT EFFECTS ON THE STABILITY OF EMULSION: EMULSION FILMS WITH ACETIC ACID AND ACETONE DIFFUSING ACROSS THE INTERFACE

The stability of emulsions is studied using, as a model of two interacting drops, an aqueous film of a surfactant immersed in an oil phase. It is shown that the mass transfer of a solute across the film changes its life-time. This change depends on several parameters as the nature and concentration of the solute. the direction of mass transfer, the time elapsed after the formation of the film. The destabilizing effect, of the transfer is found to be much less pronounced when the solute is in the continuous water phase. The instability is ascribed to the Marangoni effect and/or to liquid flow from the film drawn by diffusion of the solute.     

Studies on emulsion liquid membrane extraction of cephalexin

An experimental study on batch extraction of cephalexin using an emulsion liquid membrane system has been reported. The effects of surfactant, carrier and solute concentrations, phase volume ratio, stirring speed, and counterion concentration on the extraction rate were examined. Surfactant, carrier and diluent used were Span-80, Aliquat-336 and n-heptane–kerosene (1:1), respectively. Under the optimised experimental conditions, emulsion swelling was found to be marginal. By maintaining an appropriate pH gradient in the feed and receiving aqueous phase, facilitated transport could be realised. Selective separation of cephalexin from a mixture of 7-aminodeacetoxy cephalosporanic acid (7-ADCA) could be demonstrated in the emulsion liquid membrane system. A mathematical model based on mass transfer across aqueous boundary layer, interfacial chemical reaction and diffusion in the emulsion globule provides a reasonable fit of the experimental solute concentration versus time profiles in the emulsion liquid membrane system.     

Mass transfer of hydrophobic solutes in solvent swollen silicone rubber membranes

The mass transfer characteristics of a non-porous silicone rubber membrane contacting an aqueous and an organic phase were determined using a shell and tube mass exchanger. Firstly, the stability of the liquid/membrane interfaces was examined, and when positive aqueous phase transmembrane pressure differentials of up to 2 bar were applied, no bulk transmembrane flow of either liquid was observed. This result was not affected by the addition of surfactants or biomass to the aqueous phase, and therefore it seems that phase breakthrough, common with porous membranes, is avoided. Secondly, the mass transfer characteristics of a range of model solutes were investigated and explained with a resistances in series model. A high membrane/aqueous partition coefficient (P^mem_aq) (approximately>25) resulted in the aqueous phase film resistance limiting, whilst a low P^mem_aq (approximately<5) resulted in the membrane resistance limiting. In contact with organic solvents the silicone rubber swelled to various degrees, and this was solvent dependent. The degree of swelling, and the relative partitioning of the solute into the swelling solvent, impacted on P^mem_aq and the membrane diffusion coefficient. These two parameters could be increased by using a highly swelling solvent (solvent constituting>50% of the swollen membrane volume) with a high organic/aqueous partition coefficient (P^org_aq) for the solute. In this way the membrane resistance for some solutes was decreased, and therefore the overall mass transfer coefficient increased. Finally, the effect of the presence of other hydrophobic solutes on the rate of mass transfer was investigated, and in the case of geraniol and citronellol (two chemically similar solutes with low water solubilities, 0.7 and 0.35 g l⁻¹, respectively) the effect was similar to a “salting out” phenomena. This resulted in an increase of P^org_aq for both geraniol and citronellol, and therefore a decrease in flux of the solute transferring to the aqueous phase.     

Mass transfer across liquid—liquid interfaces : Part 2. Calculation of Mass-transfer Coefficients from Experiments with an Automated Falling-drop Apparatus

The mass transfer of 4-methoxy-N,N-dimethylbenzylamine from aqueous drops to cyclohexane was studied by the falling-drop method with computer-controlled equipment. Different contact times were achieved by letting the drop-forming device ascend or descend to previously defined levels in the column containing the continuous phase. The overall mass-transfer coefficient was evaluated from the relationship between contact time and solute concentration in the donating phase. Whether or not the continuous phase must be replaced between the measurements needed to calculate the overall mass-transfer coefficient is discussed in detail. Corrections for the gradually increasing concentration of the transported solute in the receiving phase are proposed and tested. The order of contact times (decreasing or increasing) is shown to be of great importance for these corrections.     

Method to predict the bandwidth of elution profile under the linear gradient elution in reversed‐phase HPLC

Solute migration in a chromatographic column is an important consideration when designing batch or continuous chromatographic separation processes. Most design methods for the chromatographic processes are based on the equilibrium theory which concerns only the migration velocity of the solute. However, in real cases, it is important to predict the zone spreading which occurs by axial dispersion and mass transfer resistance. To predict the actual solute profiles in the column or effluent stream, numerical methods to solve nonlinear partial differential equations have been used. However, these methods involve much time and expense. In this work, two different rate factors are considered to predict the characteristics of the solute profiles. The first is solute migration velocity and the second is the zone spreading rate. The zone spreading rate can be estimated by the apparent axial dispersion coefficient which is obtained from the height of the equivalent theoretical plate in particular. Four benzene derivatives (benzene, toluene, p‐xylene, and acetophenone) were used as model solutes, and two mobile phase systems, water/methanol and water/ACN, were used in RP‐HPLC. The bandwidths and retention times of the solutes were predicted under several linear gradient conditions. The predicted and experimental bandwidths and retention times showed good agreement.     

Membrane extraction for separation of copper cations from acid solution using polypropylene hollow fibre membrane

The membrane extraction of copper ions was carried out using hydrophobic poly(propylene) (PP) hollow fiber membrane modules and kerosene solutions containing organic extractant. The influences of different extractant on the extraction yield, mass transfer performance and mass transfer mechanism were studied. Compared with 2‐ethylhexyl phosphoric acid (2EHPA) and 2‐methyl‐5‐sulpho benzaldoxime (2M5SB), di‐(2‐ethylhexyl)phosphoric acid (D2EHPA) extractant system with high distribution coefficient exhibited higher extraction yield of 99.7%. The extraction equilibrium time, the final extraction yield and the total mass transfer coefficient were independent of the flow rates of two phases. The extraction equilibrium time and the final extraction yield at different flow rates of two phases were 80 min and near 99.5%, respectively. A mass transfer model of a complexation reaction describing the overall mass transfer resistance was controlled by interfacial reactions rather than the aqueous and organic boundary layer which could explain the effect of flow rate on the final extraction yield and the total mass transfer coefficient. This model showed that the mass transfer resistance and mass transfer coefficient were independent of Cu²⁺ when copper ion concentration was more than 0.06 g/L. However, when copper concentration was less than 0.06 g/l, the mass transfer resistance increased as Cu²⁺ concentration decreased, and the mass transfer coefficient decreased as Cu²⁺ concentration decreased. Extractant entrainment in the aqueous phase and membrane fouling were investigated primarily. It was found that the solvent entrainment could reduce to 10 ppm much lower than 200 ppm of the classic liquid–liquid extraction, and that the cleaning of contaminated membranes was not complete. However, it can be still concluded from this research that the membrane extraction in PP hollow fibre with D2EHPA extractant would be an effective and promising processing means for Cu²⁺ separation from aqueous solution. Copyright © 2005 John Wiley & Sons, Ltd.     

Monodisperse w/w/w Double Emulsion Induced by Phase Separation

We develop an approach to fabricate monodisperse water-in-water-in-water (w/w/w) double emulsion in microfluidic devices. A jet of aqueous solution containing two incompatible solutes, dextran and polyethylene glycol (PEG), is periodically perturbed into water-in-water (w/w) droplets. By extracting water out of the w/w droplet, the solute concentrations in the droplet phase increase; when the concentrations exceed the miscibility limit, the droplet phase separates into two immiscible phases. Consequently, PEG-rich droplets are formed within the single emulsion templates. These PEG-rich droplets subsequently coalesce with each other, resulting in transiently stable w/w/w double emulsions with a high degree of size uniformity. These double emulsions are free of organic solvents and thus are ideal for use as droplet-vessels in protein purification, as microreactors for biochemical reactions, and as templates for fabrication of biomaterials.     

Influence of interfacial properties on Ostwald ripening in crosslinked multilayered oil-in-water emulsions

The influence of interfacial crosslinking, layer thickness and layer density on the kinetics of Ostwald ripening in multilayered emulsions at different temperatures was investigated. Growth rates of droplets were measured by monitoring changes in the droplet size distributions of 0.5% (w/w) n-octane, n-decane, and n-dodecane oil-in-water emulsions using static light scattering. Lifshitz-Slyozov-Wagner theory was used to calculate Ostwald ripening rates. A sequential two step process, based on electrostatic deposition of sugar beet pectin onto fish gelatin or whey protein isolate (WPI) interfacial membranes, was used to manipulate the interfacial properties of the oil droplets. Laccase was added to the fish gelatin-beet pectin emulsions to promote crosslinking of adsorbed pectin molecules via ferulic acid groups, whereas heat was induced to promote crosslinking of WPI and helix coil transitions of fish gelatin. Ripening rates of single-layered, double-layered and crosslinked emulsions increased as the chain length of the n-alkanes decreased. Emulsions containing crosslinked fish gelatin-beet pectin coated droplets had lower droplet growth rates (3.1 ± 0.3 × 10⁻²⁶ m³/s) than fish gelatin-stabilized droplets (7.3 ± 0.2 × 10⁻²⁶ m³/s), which was attributed to the formation of a protective network. Results suggest that physical or enzymatic biopolymer-crosslinking of interfaces may reduce the molecular transport of alkanes between the droplets in the continuous phase.     

Emulsion liquid membranes: Role of internal droplet size distribution on toluene/n-heptane separation

Using oil/water/oil-type emulsion liquid membranes, batch wise extraction experiments are carried out to separate toluene from a mixture of toluene and n-heptane. In the separation process using emulsion liquid membranes, the internal phase polydispersity affects mass transport of a solute because under steady operating conditions, internal droplet size and size distribution are proportional to the interfacial area. The present study aims to assess the polydispersity character of the internal droplets of emulsion globules. In this paper, the important variables affecting dispersed drop sizes as well as internal droplets mean diameter and size distribution of the emulsion globule, including impeller speed during emulsification, surfactant concentration, volume ratio of surfactant solution, carrier concentration and composition of feed phase are systematically investigated.     

Extraction of uranyl ions from aqueous solutions using silica-gel-bound macrocycles for alpha contaminated waste water treatment

The efficiency for the extraction of U(VI) of new modified silica gels, namely N-tripropionate (or N-triacetate)-substituted tetraazamacrocycles-bound silica gels, has been studied. The effect of the nature of the ligand, the pH and the temperature was studied both in batch experiments as well as in continuous extraction. These silica gels are good candidates for the extraction of U(VI) when compared to a commercially available acid-type chelating resin. The breakthrough and regeneration tests showed that the total removal of U(VI) from a contaminated solution can be achieved by using a column packed with such tetraazamacrocycles-bound silica gels. Finally, the use of a modified silica gel in a pilot device allowed the total decontamination of 50 m³ of real effluents containing traces of uranium, plutonium, and americium.     

Thermal behaviour of emulsions studied by differential scanning calorimetry

This article is a review about the ways in which solidification and the melting may occur within emulsions submitted to steady cooling and heating performed in a differential scanning calorimeter. Simple, multiple and mixed emulsions are considered. Due to nucleation phenomena creating supercooled and supersaturated liquids, the DSC curves obtained during cooling and heating are quite different. The influence of a solute in the disperse phase is described in detail. Some implications about the instabilities of emulsions due to mass transfer phenomena are described.     

Behavior of lanthanides in countercurrent chromatography using dihexyl-N,N-diethylcarbamoyl methylene phosphonate as stationary phase

Counter-current chromatography is a real liquid-liquid chromatography. The retention volume of the solute can be calculated from the batch distribution ratio in organic separations. In the separations of metal ion, there are several complex and dissociation reactions involved in the two phases, and the retention volume cannot be always predicted from the batch distribution ratio. A mass transfer model is proposed in this paper and an expression of V(R) is derived. The retention volume of metal ion is determined not only by the batch distribution ratio but also by the mechanism of the extraction reaction. When 25% dihexyl-N,N-diethylcarbamoyl methylenephosphonate in cyclohexane is used as stationary phase and 2.91 mol/l HNO3 as mobile phase, the dynamic distribution ratios obtained from the chromatogram are not equal to but proportional to the batch distribution coefficients. These results are in agreement with the theoretical expression.     

Extraction and re-extraction of phenylalanine by cationic reversed micelles in hollow fibre contactors

This work reports the extraction of phenylalanine with a reversed micellar system consisting of TOMAC/hexanol/n-heptane using hydrophobic hollow fibre modules. Extraction studies were performed under different hydrodynamic conditions and mass transfer correlations for the shell and tube sides were developed. The correlations were determined using a one-step calculation method and the results obtained are in agreement with the literature for the range of Reynolds numbers studied.Based on the obtained correlations and on the resistance in series model, a transport model was developed in which the phenylalanine concentration in the feed phase can be predicted during the experimental run. For the extraction process the model developed describes satisfactorily the evolution of phenylalanine concentration with time under different hydrodynamic conditions. The re-extraction process was found to be kinetically controlled due to the higher dynamic stability of reversed micelles when contacting a stripping phase with high ionic strength. The experimental results obtained were described using a kinetic model developed.Simultaneous extraction/stripping of phenylalanine was also accomplished using two hollow fibre modules in series, using different volume phase ratios. The mass transfer process was modelled and compared with the experimental results.     

Dimensional analysis of steady state flux for microfiltration and ultrafiltration membranes

Dimensional analysis of the mass, length and time shows that the steady state flux observed for microfiltration or ultrafiltration through inorganic composite membrane can be expressed using two dimensionless numbers. The shear stress number N_S compares the shear stress against the membrane wall to the driving pressure, while the resistance number N_f compares the convective cross-flow transport to the drived transport through a layer, whose resistance is the sum of all the resistances induced by the different processes which limit the mass transport. Experimental data obtained in ultrafiltration of hydrocarbon emulsions and microfiltration of methanogenic bacteria suspensions and secondary treated wastewater were recalculated in terms of these dimensionless groups. Straight lines were plotted whose slope depends solely on the suspension and the membrane and not on the solute concentration. A negative slope and a positive intersection with the N_S axis means that a cake layer or a polarization layer can be completely eliminated at a critical cross-flow velocity; this was the case for an inorganic particles suspension and for the methanogenic suspension. A straight line of negative slope followed by a plateau means that an irreversible fouling is superimposed to the reversible phenomenon; this was observed for a secondary treated wastewater. A positive slope means that fouling predominates; this was observed with hydrocarbon emulsions.     

Mathematical modeling of penicillin G extraction in an emulsion liquid membrane system containing only a surfactant in the membrane phase

An extraction experiment of penicillin G was performed in an emulsion liquid membrane system in which only ECA 4360J exists in the organic membrane phase without a predominant carrier, Amberlite LA-2, used in our previous works and it functions as a carrier as well as a surfactant. A permeation model for the present system has been developed as a primary study to examine the transport mechanism of penicillin G in the previous batch and continuous systems with two carriers of Amberlite LA-2 and ECA 4360J. The model takes into account the mass transfer in the external aqueous film, the extraction reaction between penicillin G and ECA 4360J at the external interface, the diffusion of penicillin G in the emulsion phase, the stripping reaction at the internal interface and the pH change of internal aqueous solution containing Na₂CO₃ with penicillin G transported into the internal phase. The experimental data were well fitted with the present model. Also, an expression for the reaction of penicillin G with ECA 4360J was obtained through a series of equilibrium measurements in liquid–liquid extraction system.     

Selective membrane alternative to the recovery of zinc from hot-dip galvanizing effluents

This work reports the study of the kinetics of zinc recovery from spent pickling solutions by means of emulsion pertraction technology (EPT) in order to reuse the metal in electrolytic processes. Tributyl phosphate (TBP) and service water were used as extraction (EX) and back-extraction (BEX) agents, respectively. Kinetic experiments were carried out in hollow fiber membrane contactors in order to analyse the influence of several operation variables on the rate of zinc recovery. A mathematical model that considers the mass transfer resistance shared between the organic liquid membrane and the organic phase boundary layer was developed; the mass transfer coefficients were estimated by means of the parameter estimation tool ASPEN CUSTOM MODELER (from ASPENTECH) to obtain the values k_m = 2.68 × 10⁻⁷ m/s and A_Vk_o = 0.0125 s⁻¹. Simulated results agreed satisfactorily well with experimental data. Consequently, the kinetic model and parameters were confirmed. Finally, a comparison between EPT and non-dispersive solvent extraction (NDSX) was carried out in order to evaluate the advantages and disadvantages of both membrane configurations.     

Further studies on solvent extraction with immobilized interfaces in a microporous hydrophobic membrane

Investigations on solvent extraction of acetic acid into xylene or methyl isobuty] ketone by using immobilized interfaces in microporous hydrophobic membranes have now been extended to a number of different membranes with a wide variation in pore size and porosity. Measured intrinsic membrane transfer coefficients of the solute are adequately described by the simple model of unhindered diffusion in tortuous pores developed earlier. Applied pressure difference did not influence the overall solute transfer coefficient as long as it was not close to that required for the breakthrough of aqueous phase into organic phase. Aqueous and organic boundary layer mass transfer coefficients in the flow type test cell have been determined with a known membrane and utilized to predict effectively the overall solute transfer coefficient observed with other membranes.     

How does a CC double bond cleave in the gas phase? Fragmentation of protonated ketotifen in mass spectrometry

In the literature, it is reported that the protonated ketotifen mainly undergoes C?C double bond cleavage in electrospray ionization tandem mass spectrometry (ESI‐MS/MS); however, there is no explanation on the mechanism of this fragmentation reaction. Therefore, we carried out a combined experimental and theoretical study on this interesting fragmentation reaction. The fragmentation of protonated ketotifen (m/z 310) always generated a dominant fragment ion at m/z 96 in different electrospray ionization mass spectrometers (ion trap, triple quadrupole and linear trap quadrupole (LTQ)‐orbitrap). The mechanism of the generation of this product ion (m/z 96) through the C?C double bond cleavage was proposed to be a sequential hydrogen migration process (including proton transfer, continuous two‐step 1,2‐hydride transfer and ion‐neutral complex‐mediated hydride transfer). This mechanism was supported by density functional theory (DFT) calculations and a deuterium labeling experiment. DFT calculations also showed that the formation of the product ion m/z 96 was most favorable in terms of energy. This study provides a reasonable explanation for the fragmentation of protonated ketotifen in ESI‐MS/MS, and the fragmentation mechanism is suitable to explain other C?C double bond cleavage reactions in mass spectrometry. Copyright © 2016 John Wiley & Sons, Ltd.