Dilute Aqueous Mixtures Research Articles

Ethyl trifluoroacetate formation as a means to recover trifluoroacetic acid from dilute aqueous mixture: reaction, separation and purification

ABSTRACT Recovery of trifluoroacetic acid (TFA) by distillation is difficult due to the existence of a high boiling azeotrope. Esterification of TFA to ethyl trifluoroacetate was performed in this work in order to recover the acid from its dilute aqueous mixture. The reaction was carried out in a batch reactor. Parameter estimation was done to obtain a kinetic model by using the experimental data. Reactive distillation studies were performed to explore its feasibility and process intensification. Methodology to obtain almost pure ethyl trifluoroacetate from dilute aqueous reaction mixture was devised.

Temperature, Pressure, and Concentration Derivatives of Nonpolar Gas Hydration: Impact on the Heat Capacity, Temperature of Maximum Density, and Speed of Sound of Aqueous Mixtures.

The hydrophobic effect is an umbrella term encompassing a number of solvation phenomena associated with solutions of nonpolar species in water, including the following: a meager solubility opposed by entropy at room temperature; large positive hydration heat capacities; positive shifts in the temperature of maximum density of aqueous mixtures; increases in the speed of sound of dilute aqueous mixtures; and negative volumes of association between interacting solutes. Here we present a molecular simulation study of nonpolar gas hydration over the temperature range 273.15-373.15 K and a pressure range -500 to 1000 bar to investigate the interrelationships between distinct hydrophobic phenomena. We develop a new free energy correlation for the solute chemical potentials founded on the Tait equation description of the equation-of-state of liquid water. This analytical correlation is shown to provide a quantitatively accurate description of nonpolar gas hydration over the entire range of thermodynamic state points simulated, with an error of ∼0.02 kBT or lower in the fitted chemical potentials. Our simulations and the correlation accurately reproduce many of the available experimental results for the hydration of the solutes examined here. Moreover, the correlation reproduces the characteristic entropies of hydration, temperature dependence of the hydration heat capacity, perturbations in the temperature of maximum density, and changes in the speed of sound. While negative volumes of association result from pairwise interactions in solution, beyond the limits of our simulations performed at infinite dilution, we discuss how our correlation could be supplemented with second virial coefficient information to expand to finite concentrations. In total, this work demonstrates that many distinct phenomena associated with the hydrophobic effect can be captured within a single thermodynamically consistent correlation for solute hydration free energies.

PH-responsive micellization of an amine oxide surfactant with branched hydrophobic tail

pH-sensitive surfactants find applications in many fields, including responsive drug delivery and smart material design. The rational design of the surfactant molecular structure leads to species presenting strong variations of the micellization parameter (e.g., critical micelle concentration, cmc, and aggregate dimension) in a controlled pH range.In the present work, the micellization of the branched amine oxide surfactant N,N-dimethyl-2-propylheptan-1-amine oxide (C10DAO-branched) is studied as a function of pH in dilute aqueous mixtures. Its behavior is compared with that of the linear isomer N,N-dimethyldecan-1-amine oxide (C10DAO-linear). The samples are investigated by potentiometric titrations, fluorescence spectroscopy, and Dynamic Light Scattering (DLS). With increasing pH, micellized C10DAO-branched presents a higher tendency to remain in the protonated/cationic form with respect to the linear isomer. As a consequence, the minimum cmc value, observed when the protonated and the deprotonated/zwitterionic forms of the surfactant coexist in the micelles, is shifted to higher pH values. The volume of these C10DAO-branched “mixed micelles” is more than one order of magnitude higher than that of completely protonated or deprotonated aggregates. This is a singularity of the branched surfactant, not observed for the linear isomer. Overall, the results highlight that the branched molecular architecture of the surfactant tail, favoring the formation of low-curvature aggregates, enhances H-bonding between the protonated and deprotonated headgroups, which synergistically stabilizes the flatter surface of bulkier aggregates.Taking into account the good biodegradability of surfactants with a limited number of short side chains, purposely designed branched surfactants appear as a suitable option to accurately tune supramolecular aggregation in pH-responsive formulations.

Probabilistic latent semantic analysis of composite excitation-emission matrix fluorescence spectra of multicomponent system.

In the present work, a simple and fast analytical procedure involving minimum user intervention was developed by combining the excitation-emission matrix fluorescence (EEMF) spectroscopy with Probabilistic latent semantic analysis (pLSA) technique. Akaike Information Criterion (AIC) was used to enable the user to automatically select the optimum model for analysing the mixtures of fluorescent components. The utility of the present work was successfully evaluated by analysing the dilute aqueous mixtures of certain fluorescent molecule such as Catechol, Hydroquinone, Indole, Tryptophan and Tyrosine of biological relevance. The developed AIC assisted pLSA model of five components explained >90% variance of spectral data sets. The identity between the pLSA retrieved spectral profiles was established using similarity index (SI) parameter in automatic manner. The SI values were found to be close to unit values for each of the five analyzed molecules. The regression parameter between the actual and pLSA predicted concentrations were found to be well within acceptable limits. Both root mean square of calibration and predictions for each of the five fluorescent molecules were found to be <1%, whereas, the square of the correlation coefficient (R2) value was found to be >0.98 suggesting the developed pLSA model was quite precise in analysing both calibration and validation set samples. The uniqueness of the developed pLSA model for EEMF spectroscopic data was successfully tested using the sequential quadratic programming (SQP) algorithm. The differences between the upper and lower bands in SQP were found to be ≤0.005. In summary, the proposed approach serve as swift and simple analytical tool for the analysis of fluorescent mixtures without involving pre-separation step.

Fractionation of a dilute acetic acid aqueous mixture in a continuous countercurrent packed column using supercritical CO2: Experiments and simulation of external extract reflux

Fractionation of dilute acetic acid aqueous mixtures was operated using a continuous countercurrent packed column with supercritical CO2. A generic procedure was developed to assess the feasibility of such an operation. Experiments were performed using a 2 m high and 17 mm inner diameter column, in the range (10−15 MPa) and (40 °C–60 °C). Thermodynamics of the mixture was described using the Soave-Redlich-Kwong equation modified by Boston Mathias with PSRK mixing rules and UNIQUAC activity coefficient model. Experimental results were compared to simulation using a software based on the concept of equilibrium stage. Conventional liquid-liquid extraction methods indicated that thermodynamics limits the separation performances. Therefore, an external extract reflux configuration was tested by simulation. It was shown that the limitation could be overridden and influence of design (number of stages, position of the feed) and operating conditions (reflux ratio, solvent-to-feed ratio) has been assessed.

Non-negative Factor (NNF) Assisted Partial Least Square (PLS) Analysis of Excitation-Emission Matrix Fluorescence Spectroscopic Data Sets: Automating the Identification and Quantification of Multifluorophoric Mixtures.

Excitation-emission matrix fluorescence spectroscopy is simple and sensitive techniques that generate the composite fluorescence fingerprints. EEMF can be used for the identification and quantification of the fluorophores without involving any pre-separation step provided a suitable data analysis approach is applied. In the present work, non-negative factor (NNF) assisted partial least square (PLS) analysis is used for the analysis of EEMF data sets acquired for the dilute aqueous mixtures of fluorophores. The proposed approach allows automatic selection of the optimum number of factors for NNF analysis by incorporating the Akaike information criterion. The proposed approach also incorporates the spectral correlation analysis for the automatic identification of the NNF retrieved EEMF spectral profiles. The NNF retrieved contribution values along with their real concentration values are subjected to PLS analysis to develop a calibration model. The proposed approach was successfully tested using EEMF data acquired for the dilute aqueous mixtures of Catechol, Hydroquinone, Indole, Tryptophan and Tyrosine. The results were evaluated using the various statistical parameters and each of them found to well within the expected limits. In summary, NNF assisted PLS analysis of EEMF technique allows automatized analysis of the multifluorophoric mixtures with minimum user inputs.

Discrete Wavelet Transform (DWT) Assisted Partial Least Square (PLS) Analysis of Excitation-Emission Matrix Fluorescence (EEMF) Spectroscopic Data Sets: Improving the Quantification Accuracy of EEMF Technique.

In the present work, it is shown that quantitative estimation efficiency of the partial least square (PLS) calibration model can be significantly improved by pre-processing the EEMF with discrete wavelet transform (DWT) analysis. The application of DWT essentially reduces the volume of data sets retaining all the analytically relevant information that subsequently helps in establishing a better correlation between the spectral and concentration data matrices. The utility of the proposed approach is successfully validated by analyzing the dilute aqueous mixtures of four fluorophores having significant spectral overlap with each other. The analytical procedure developed in the present study could be useful for analyzing the environmental, agricultural, and biological samples containing the fluorescent molecules at low concentration levels.

Composite Membranes with a Polyvinyltrimethylsilane Skin Layer for Separation of Water–Alcohol Mixtures

The paper presents the characteristics of a laboratory-made water-selective composite membrane with a selective layer of hydrophobic polyvinyltrimethylsilane (PVTMS) for use in the processes of vapor-phase membrane recovery of alcohols from dilute aqueous alcohol mixtures of biogenic origin. The support is a polyacrylonitrile ultrafiltration membrane, and the PVTMS skin layer of the resulting composite membrane has a thickness of 3 to 4 microns. The vapor transport and separation characteristics of the membrane for water–ethanol and water–butanol mixtures in the temperature range of 60–80°C have been studied. It has been shown that the membrane selectivity varies in the range of 23–39 for the water/ethanol pair or 100–140 for the water/butanol pair. A specific feature of the hydrophobic water-selective membrane as applied to the vapor-phase process is the stability of its characteristics due to the absence of swelling, in contrast to hydrophilic water-selective membranes whose characteristics substantially depend on the activity of water vapor. The process of vapor-phase membrane recovery of ethanol and butanol from dilute aqueous alcohol mixtures of biogenic origin with their initial concentrations of 10 and 1 wt %, respectively, has been mathematically modeled on the basis of the experimental data. The calculation results show that the composite membrane obtained makes it possible to concentrate ethanol and butanol to 95 and 98 wt % with degrees of recovery of more than 0.8 and more than 0.9, respectively.

Random initialisation of the excitation-emission matrix fluorescence spectral variables in constraint fashion for subsequent multivariate curve resolution alternating least square analysis on a peculiarly designed calibration set: Simultaneous sensing of nine polycyclic aromatic hydrocarbons in water samples

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic and mutagenic in nature therefore their sensing in water sample is an important analytical task. In the present work, a novel approach that is based on the random initialisation of the excitation-emission matrix fluorescence (EEMF) spectral variables in constraint fashion for subsequent multivariate curve resolution alternating least Square (MCR-ALS) analysis is introduced for simultaneously sensing the complex dilute aqueous mixture of PAHs. The usefulness of the proposed analytical approach is successfully demonstrated by applying it intentionally on a calibration set that is peculiar in many senses. The peculiarity mainly arises because the designed (i) the calibration set consist of nine PAHS having significant spectral overlap, (ii) the concentration of each PAH in different samples are kept constant and (iii) any two samples differ only in the presence and absence of the PAHs. The proposed approach is found to make precise and accurate estimation of each of the nine PAHs without involving any pre-separation. In summary, the proposed approach provides a simple and cost-effective procedure for simultaneous sensing of several PAHs in water samples. The proposed approach could be very useful in developing countries.

Application of Genetic Algorithm (GA) Assisted Partial Least Square (PLS) Analysis on Trilinear and Non-trilinear Fluorescence Data Sets to Quantify the Fluorophores in Multifluorophoric Mixtures: Improving Quantification Accuracy of Fluorimetric Estimations of Dilute Aqueous Mixtures.

Excitation-emission matrix fluorescence (EEMF) and total synchronous fluorescence spectroscopy (TSFS) are the 2fluorescence techniques that are commonly used for the analysis of multifluorophoric mixtures. These 2fluorescence techniques are conceptually different and provide certain advantages over each other. The manual analysis of such highly correlated large volume of EEMF and TSFS towards developing a calibration model is difficult. Partial least square (PLS) analysis can analyze the large volume of EEMF and TSFS data sets by finding important factors that maximize the correlation between the spectral and concentration information for each fluorophore. However, often the application of PLS analysis on entire data sets does not provide a robust calibration model and requires application of suitable pre-processing step. The present work evaluates the application of genetic algorithm (GA) analysis prior to PLS analysis on EEMF and TSFS data sets towards improving the precision and accuracy of the calibration model. The GA algorithm essentially combines the advantages provided by stochastic methods with those provided by deterministic approaches and can find the set of EEMF and TSFS variables that perfectly correlate well with the concentration of each of the fluorophores present in the multifluorophoric mixtures. The utility of the GA assisted PLS analysis is successfully validated using (i) EEMF data sets acquired for dilute aqueous mixture of four biomolecules and (ii) TSFS data sets acquired for dilute aqueous mixtures of four carcinogenic polycyclic aromatic hydrocarbons (PAHs) mixtures. In the present work, it is shown that by using the GA it is possible to significantly improve the accuracy and precision of the PLS calibration model developed for both EEMF and TSFS data set. Hence, GA must be considered as a useful pre-processing technique while developing an EEMF and TSFS calibration model.

Rate-based simulation of a high pressure counter-current packed column for supercritical CO2 extraction of alcohol from dilute aqueous mixtures

In this work, the modeling and simulation of a fractionation packed column for the recovery of isopropanol from dilute aqueous mixtures using supercritical CO2 is presented. The model is based on the numerical resolution of differential mass balances for each component over the column height. The multicomponent mass transfer between phases is described using a “rate-based” approach and the concept of local mass transfer coefficients. The model was validated by reproduction of experimental steady-state results for the fractionation of 5% isopropanol aqueous solutions obtained in a bench scale counter-current column. The effect of process conditions on the separation performance was satisfactorily described by the model calculations, showing that operation pressure and CO2 flow rate enhance IPA recovery and extract purity, while operation temperature has a negative effect. Model deviations (AARD) were in all cases lower than 20%.

Thermocapillary modulation of self-rewetting films

Whereas surface tension decreases linearly with temperature for most fluids, here we consider those that exhibit a well-defined minimum. Specifically, our study is motivated by dilute aqueous mixtures of long-chain alcohols, for which surface tension is typically assumed to be a quadratic function of temperature. Utilization of these so-called ‘self-rewetting fluids’ has grown significantly in the past decade, due to observations that heat transfer is enhanced in applications such as film boiling and pulsating heat pipes. With similar applications in mind, we investigate the dynamics of a thin film with quadratic surface tension which is subjected to a temperature modulation in the bounding gas. A model is developed within the framework of the long-wave approximation, and a time-averaged thermocapillary driving force for destabilization is uncovered that results from the nonlinear surface tension. Linear stability analysis of the nonlinear partial differential equation for the film thickness is used to determine the critical conditions at which this driving force destabilizes the film and numerical investigation of this evolution equation reveals that linearly unstable perturbations saturate to regular periodic solutions (when the modulational frequency is set properly). Properties of these flows such as bifurcation at critical points and long-domain flows, where multiple unstable linear modes interact, are also discussed.

A spectrophotometric study of the complexation between methylene blue dye and sodium alginate

It was spectrophotometrically determined that dilute aqueous mixtures of methylene blue cationic dye with sodium alginate are stable self-assembling systems from dissolved state noncovalent complexes. The influence of the mixture components, the molecular weight of sodium alginate and composition of the environment on the binding ability of the polymer toward to dye were investigated. The critical pH values and also amounts of inorganic salts, an oppositely charged polyelectrolyte and an organic solvent, causing a complete inhibition of complex formation and the release of dye were determined.

Very high flux MFI membranes for alcohol recovery via pervaporation at high temperature and pressure

Abstract Ultra-thin MFI membranes (0.5 μm) were evaluated for recovery of alcohols from dilute aqueous mixtures by pervaporation at high temperature and pressure for the first time. The feed pressure was sufficiently high to keep the feed in liquid state at high temperature, while the permeate pressure was kept at atmospheric and a low flow of sweep gas was used to reduce the partial pressure on the permeate side. Atmospheric pressure on the permeate side is more practical than vacuum. High feed temperature and pressure result in high fugacity in the liquid feed, which, in combination with lower permeate pressure, results in a large driving force. Consequently, the membrane exhibited very high fluxes for feeds comprised of 10 wt% ethanol/water and 5 wt% n-butanol/water mixtures at 110 °C and 140 °C, respectively. The flux observed for 10 wt% ethanol/water mixtures was as high as about 52 kg m−2 h−1, i.e., 6 times higher than the highest previously reported flux for this separation using zeolite membranes in pervaporation. For 5 wt% n-butanol/water mixtures, the flux was 40 kg m−2 h−1, which is 11 times higher than the highest previously reported flux for this separation by zeolite membranes. At these conditions, the membrane displayed separation factors for ethanol/water and n-butanol/water mixtures of 5 and 16, respectively. However, after about 6 h of operation, the separation factor decreased significantly and the flux increased due to formation of defects in the membrane when the feed was saturated with silica. Lower membrane stability was observed for silica free feeds. The work has shown that it is possible to obtain high flux in pervaporation by using ultra-thin membranes in combination with high feed temperature. The observed membrane selectivity was not excellent, due to pressure drop over the support as well as likely concentration polarisation on the feed side resulting from the high flux. Membrane stability was also an issue at these conditions, however it was shown that stability could be improved by saturating the feed with silica.

Mixtures of amino-acid based ionic liquids and water.

New ionic liquids (ILs) involving increasing numbers of organic and inorganic ions are continuously being reported. We recently developed a new force field; in the present work, we applied that force field to investigate the structural properties of a few novel imidazolium-based ILs in aqueous mixtures via molecular dynamics (MD) simulations. Using cluster analysis, radial distribution functions, and spatial distribution functions, we argue that organic ions (imidazolium, deprotonated alanine, deprotonated methionine, deprotonated tryptophan) are well dispersed in aqueous media, irrespective of the IL content. Aqueous dispersions exhibit desirable properties for chemical engineering. The ILs exist as ion pairs in relatively dilute aqueous mixtures (10 mol%), while more concentrated mixtures feature a certain amount of larger ionic aggregates.

Binding interaction and gelation in aqueous mixtures of poly(N-isopropylacrylamide) and hectorite clay.

The binding interaction between poly(N-isopropylacrylamide) (PNIPAm) chains and hectorite clay platelets was directly detected by quartz crystal microbalance with dissipation (QCM-D) to explore the cross-linking mechanism in the strong nanocomposite hydrogel (NC gel), which is in situ polymerized with NIPAm in the clay suspension. PNIPAm chains were allowed to be adsorbed on the gold surface of the QCM electrode. A large frequency shift Δf in the QCM as introducing the clay indicated that a large amount of clay platelets were adsorbed on the deposited PNIPAm layer. The relationship between the dissipation shift ΔD and Δf revealed that the adsorption included two steps of fast initial buildup and following densification of the clay platelets. In dilute aqueous mixtures, the PNIPAm chain and clay formed aggregates as observed from the hydrodynamic diameter. A gelation state diagram was established for concentrated aqueous PNIPAm-clay mixtures. The Raman spectrum pointed out the conformation change of the PNIPAm chains in aqueous solutions when the clay was added, which would be caused by the adsorption of PNIPAm chains to the clay platelets.

Sampling of Organic Solutes in Aqueous and Heterogeneous Environments Using Oscillating Excess Chemical Potentials in Grand Canonical-like Monte Carlo-Molecular Dynamics Simulations.

Solute sampling of explicit bulk-phase aqueous environments in grand canonical (GC) ensemble simulations suffer from poor convergence due to low insertion probabilities of the solutes. To address this, we developed an iterative procedure involving Grand Canonical-like Monte Carlo (GCMC) and molecular dynamics (MD) simulations. Each iteration involves GCMC of both the solutes and water followed by MD, with the excess chemical potential (μex) of both the solute and the water oscillated to attain their target concentrations in the simulation system. By periodically varying the μex of the water and solutes over the GCMC-MD iterations, solute exchange probabilities and the spatial distributions of the solutes improved. The utility of the oscillating-μex GCMC-MD method is indicated by its ability to approximate the hydration free energy (HFE) of the individual solutes in aqueous solution as well as in dilute aqueous mixtures of multiple solutes. For seven organic solutes: benzene, propane, acetaldehyde, methanol, formamide, acetate, and methylammonium, the average μex of the solutes and the water converged close to their respective HFEs in both 1 M standard state and dilute aqueous mixture systems. The oscillating-μex GCMC methodology is also able to drive solute sampling in proteins in aqueous environments as shown using the occluded binding pocket of the T4 lysozyme L99A mutant as a model system. The approach was shown to satisfactorily reproduce the free energy of binding of benzene as well as sample the functional group requirements of the occluded pocket consistent with the crystal structures of known ligands bound to the L99A mutant as well as their relative binding affinities.

Analysis of dilute aqueous multifluorophoric mixtures using excitation–emission matrix fluorescence (EEMF) and total synchronous fluorescence (TSF) spectroscopy: A comparative evaluation

Excitation-emission matrix fluorescence (EEMF) and total synchronous fluorescence (TSF) spectroscopy are two conceptually different fluorescence techniques that have been used to map the fluorescence responses of the fluorophores present in a multifluorophoric mixture. EEMF was introduced four decades back and most of the fluorimeters have the suitable computer program which allows the acquisition EEMF spectra. Recently introduced TSF spectroscopy has been shown to possess good application potential in analytical fluorimetry and has started attracting the attention of analytical chemists. TSF data structure, however, is intrinsically different from EEMF data structure and a better understanding of TSF data structure is crucial to utilising its application potential. In the present work, a comprehensive comparative study between EEMF and TSF spectroscopic data set was performed by taking aqueous mixtures containing low concentrations of benzo[a]pyrene, chrysene, and pyrene as test case. The EEMF and TSF data structures were clearly explained by taking pyrene as an example. The effects of Rayleigh and Raman scattering on the quality of EEMF and TSF data sets were studied. EEMF and TSF data sets of dilute aqueous mixtures of benzo[a]pyrene, chrysene, and pyrene were subjected to three chemometric techniques PARAFAC, N-PLS, and MCR-ALS analysis. TSF data set in particular was found to be highly attuned to MCR-ALS analysis. Obtained results of chemometric analyses on EEMF and TSF data sets show that TSF data of dilute aqueous mixtures provides more accurate spectral and concentration information than EEMF data sets. Therefore, TSF spectroscopy could be considered as an alternate to the EEMF for the analyses of dilute multifluorophoric mixtures.

Responsive release of polyanions from soluble aggregates formed with a hydrolyzable cationic surfactant and a nonionic surfactant

Soluble aggregates formed in dilute aqueous mixtures of polyacrylate (PA), the cationic surfactant decyl betainate (DB), and the nonionic surfactant octaethylene glycol monododecyl ether (C12E8) have been characterized. The aggregates formed can be viewed as mixed micelles of DB and C12E8 with the cationic charge of DB being largely neutralized by PA condensed on the micellar surface. DB contains an ester bond that is susceptible to base-catalyzed hydrolysis under mild alkaline conditions and degradation of DB leads to a decreased attraction of PA to the mixed micelles. It is shown that (1) an increasing extent of DB hydrolysis gives a gradual increase in the fraction of PA released from the mixed aggregates to the surrounding solution, and (2) the rate of hydrolysis, and thus the rate of polymer release, can be controlled by pH. The presented principle can potentially be used in controlled release devices.

Supramolecular Organization in Self-Assembly of Chromatin and Cationic Lipid Bilayers is Controlled by Membrane Charge Density

In this work we have investigated the structures of aggregates formed in model systems of dilute aqueous mixtures of "model chromatin" consisting of either recombinant nucleosome core particles (NCPs) or nucleosome arrays consisting of 12 NCPs connected with 30 bp linker DNA, and liposomes made from different mixtures of cationic and zwitterionic lipids, 1,2-dioleoyl-3-trimethylammonium-propane chloride salt (DOTAP) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). The aggregates formed were characterized using different optical microscopy methods and small-angle X-ray scattering (SAXS), and the results are discussed in terms of the competing intermolecular interactions among the components. For a majority of the samples, the presence of lamellar structures could be identified. In samples with high fractions of DOTAP in the liposomes, well-defined lamellar structures very similar to those formed by the corresponding lipid mixtures and DNA alone (i.e., without histone proteins) were observed; in these aggregates, the histones are expelled from the model chromatin. The findings suggest that, with liposomes containing large fractions of cationic lipid, the dominating driving force for aggregation is the increase in translational entropy from the release of counterions, whereas with lower fractions of the cationic lipid, the entropy of mixing of the lipids within the bilayers results in a decreased DNA-lipid attraction.