Theory of interfacial phase transitions in surfactant systems

The spin-1 Ising model, which is equivalent to the three-component lattice gas model, is used to study wetting transitions in three-component surfactant systems consisting of an oil, water, and a nonionic surfactant. Phase equilibria, interfacial profiles, and interfacial tensions for three-phase equilibrium are determined in mean field approximation, for a wide range of temperature and interaction parameters. Surfactant interaction parameters are found to strongly influence interfacial tensions, reducing them in some cases to ultralow values. Interfacial tensions are used to determine whether the middle phase, rich in surfactant, wets or does not wet the interface between the oil-rich and water-rich phases. By varying temperature and interaction parameters, a wetting transition is located and found to be of the first order. Comparison is made with recent experimental results on wetting transitions in ternary surfactant systems.This paper is dedicated to J. K. Percus in honor of his 65th birthday.     

ENSTAR detector forη- mesic studies

We have initiated a search for a new type of nuclear matter, theη-mesic nucleus, using beams from the multi-GeV hadron facility, COSY at Juelich, Germany. A large acceptance scintillator detector, ENSTAR has been designed and built at BARC, Mumbai and fully assembled and tested at COSY. A test run for calibration and evaluation has been completed. In this contribution we present the design and technical details of the ENSTAR detector and how it will be used to detect protons and pions (the decay products ofη-mesic bound state). The detector is made of plastic scintillators arranged in three concentric cylindrical layers. The readout of the detectors is by means of optical fibres. The layers are used to generate ΔE –E spectra for particle identification and total energy information of stopped particles. The granularity of the detector allows for position (θ and ?ø determination making the event reconstruction kinematically complete     

Studies on the extraction behaviour of plutonium(IV) from mixed aqueous-organic media with sulphoxides

Extraction behaviour of plutonium (IV) from nitric acid media by two long-chain aliphatic sulphoxides, namely, di-n-hexylsulphoxide and di-n-octylsulphoxide has been investigated in the presence of several water-miscible organic solvents to study their possible synergistic effect on metal ion extraction. Methanol, ethanol, n-and iso-propanol, dioxane, acetone as well as as acetonitrile were used as the organic component of the mixed (polar) phase. These additives affected the extraction to varying degrees. Thus, extractability of Pu increases 2–3 fold with increasing concentration (upto 20%) of acetonitrile, acetone, methanol and ethanol while it decreases with increasing concentration of n-and isopropanol. At high concentration of the former, synergism changes into antagonism. Possible reasons for such behaviour are briefly discussed. Among these organic additives, maximum enhancement in the extraction of Pu(IV) was observed in the presence of acetonitrile. The relative increase in extraction was found to be more at lower sulphoxide concentrations.     

Facilitated phosphatidylserine flip-flop across vesicle and cell membranes using urea-derived synthetic translocases

Tris(2-aminoethyl)amine derivatives with appended urea and sulfonamide groups are shown to facilitate the translocation of fluorescent phospholipid probes and endogenous phosphatidylserine across vesicle and erythrocyte cell membranes. The synthetic translocases appear to operate by binding to the phospholipid head groups and forming lipophilic supramolecular complexes which diffuse through the non-polar interior of the bilayer membrane.     

Aqueous polymerization of methacrylamide

The aqueous polymerization of methacrylamide (I) initiated by KBrO₃–thioglycolic acid (TGA) has been studied at 30 ± 0.2°C in nitrogen. The rate is given by K[M]^1.19 [thioglycolic acid]¹ [KBrO₃]^0.53 for 10–15% conversion. Activation energy was found to be 53.96 kJ/mole (12.92 kcal/mole) in the investigated range of temperature 30–45°C. The role of addition of a series of aliphatic alcohols and some salts was also determined. The kinetics of polymerization was followed iodometrically.     

Studies on polymerization of vinyl acetate using ylide as an initiator and degradative transfer agent

Polymerization of vinyl acetate initiated by β-picolinium p-chlorophenacylide was carried out at 30, 35, and 40°C, using conventional dilatometric technique. The initiator and the monomer exponent values were 0.80 ± 0.15 and unity, respectively. The polymerization was inhibited in the presence of hydroquinone, but was favored by nonpolar solvent and polymerization temperature. The energy of activation was 90.3 KJ mol^?1. An average value of k/k_t for the present system was found to be 0.37 × 10^?2. The results are explained in terms of a radical mode of polymerization with degradative initiator transfer; the principal mode of termination, however, was bimolecular.     

Is collision-induced dissociation of low-energy carbonyl sulfide cations adversely affected by asymmetry?

We have measured relative abundances of fragment ions resulting from collision-induced dissociation of OCS(+) ions in collision with xenon neutrals as a function of ion kinetic energy and scattering angle. The lowest energy dissociation product, S(+), dominates at all energies up to 53 eV kinetic energy studied here. Surprisingly, the second most abundant dissociation channel is CS(+) and not CO(+) even though the thermochemical threshold for CO(+) is lower than that for CS(+) and CO(+) is more abundant than CS(+) in the normal mass spectrum of OCS. We do not observe any significant abundance of CO(+) in this energy range, suggesting that collision-induced excitation and dissociation of OCS(+) is significantly different to that of symmetric triatomic ions. A possible role of asymmetry in the molecular ion's collisional activation via neutral collision is suggested for the different behavior.     

Importance of micellar kinetics in relation to technological processes

The association of many classes of surface-active molecules into micellar aggregates is a well-known phenomenon. Micelles are in dynamic equilibrium, constantly disintegrating and reforming. This relaxation process is characterized by the slow micellar relaxation time constant, tau(2), which is directly related to the micellar stability. Theories of the kinetics of micelle formation and disintegration have been discussed to identify the gaps in our complete understanding of this kinetic process. The micellar stability of sodium dodecyl sulfate micelles has been shown to significantly influence technological processes involving a rapid increase in interfacial area, such as foaming, wetting, emulsification, solubilization, and detergency. First, the available monomers adsorb onto the freshly created interface. Then, additional monomers must be provided by the breakup of micelles. Especially when the free monomer concentration is low, which is the case for many nonionic surfactant solutions, the micellar breakup time is a rate-limiting step in the supply of monomers. The Center for Surface Science & Engineering at the University of Florida has developed methods using stopped flow and pressure jump with optical detection to determine the slow relaxation time of micelles of nonionic surfactants. The results showed that the ionic surfactants such as SDS exhibit slow relaxation times in the range from milliseconds to seconds, whereas nonionic surfactants exhibit slow relaxation times in the range from seconds (for Triton X-100) to minutes (for polyoxyethylene alkyl ethers). The slow relaxation times are much longer for nonionic surfactants than for ionic surfactants, because of the absence of ionic repulsion between the head groups. The observed relaxation times showed a direct correlation with dynamic surface tension and foaming experiments. In conclusion, relaxation time data of surfactant solutions correlate with the dynamic properties of the micellar solutions. Moreover, the results suggest that appropriate micelles with specific stability or tau(2) can be designed by controlling the surfactant structure, concentration, and physicochemical conditions (e.g., salt concentration, temperature, and pressure). One can also tailor micelles by mixing anionic/cationic or ionic/nonionic surfactants for a desired stability to control various technological processes.