폴리옥시에틸렌(POE) 계열에서 두 번째로 작은 화합물인 양친매 분자 2-(2-hexyloxyethoxy) ethanol (C6E2) 수용액의 밀도를 측정하였다. 밀도 측정은 진통 튜브 밀도계를 이용하여 279.15 K와 282.15 K에서 이루어졌다. 측정된 밀도로부터 2성분 계 C6E2 (1)/H2O (2)의 과잉 부피와 부분 몰 부피를 결정하였다. 과잉 부피는 음의 편차를 나타내었으며, C6E2의 몰 분율 χ ≃ 0.45에서 최소 값을 나타내었다. C6E2 와 물 분자 사이에 끌어당기는 작용이 상대적으로 우월하지만, χ ≃ 0.45 에서 이 작용이 가장 크다는 사실을 말해준다. 2성분 계 C6E2 (1)/H2O (2)에서 부분 몰 부피 V1 는 몰 분율 χ 에 따라서 단조 증가하였으며, V2 는 감소하였다. V1 과 V2 에서 C6E2 분자들의 회합을 암시하는 특이점은 관찰되지 않았다.
Any theory of liquid should account for interactions between molecules, since molecules in a liquid are close to each other. For this matter statistical-mechanical methodology has been used and various models have been proposed on the basis of this methodology. Among them Kirkwood-Buff solution theory has attracted a lot of interest, because it is regarded as being the most powerful. In this article Kirkwood-Buff solution theory is revisited and its key equations are derived. On the way to these equations, the concepts of pair correlation function, radial distribution function, Kirkwood-Buff integration are explained and implemented. Since complexity of statical mechanics involved in this theory, the equations are applied to one-component systems and the results are compared to those obtained by classical thermodynamics. This may be a simple way for Kirkwood-Buff solution theory to be examined for its validity.
Three-dimensional, statistical-mechanical formulations of problems are usually untractable analytically, and therefore they are commonly solved numerically. However, their one-dimensional counterparts are always to be solved analytically. In general analytical solutions sheds more insights to the problems than numerical solutions. Hence, solutions of one-dimensional problems may provide key properties to the problems, when they are extended to three dimensions. In this article, thermodynamic properties of one-dimensional fluid comprising molecules of rigid rods are analyzed statistical-mechanically. Molecules of rigid rods are characterized with repulsive or excluded volume effect. It is observed that this feature is well reflected in thermodynamic functions such as Helmholtz free energy. volumetric equation of state. chemical potential, entropy, etc.
In this article a reliable and rapid method based on specific turbidimetry is proposed for the determination of sizes of nanoparticles. Conventionally in specific turbidimetry specific turbidities for a colloidal dispersion are measured as a function of light wavelength, and compared to theoretical values calculated from Mie scattering theory for presumed particle sizes. In contrast specific turbidity at a fixed wavelength is measured in the proposed method, and particle sizes are determined from the prepared calibration curve. The calibration curve is a plot of specific turbidity vs particle size and in this case the specific turbidities are measured for a couple of samples of known sizes.
This article investigated to polymer-clay nanocomposite, especially in interfacial respect clay structure, its dispersion into polymer matrix, and clay modification is studied. The cationic exchange of surfactants with clay gallery results in preparing organo-clay capable of compatiblizing to monomer or polymer and increasing interlayer adhesion energy due to expansion of interlayer spacing. The orientation of surfactant in clay gallery is affected by chemical structure and charge density of clay, and interlayer spacing and volume is increased with alkyl chain length of surfactant, or charge density of clay. Also, the interaction between clay and polymer in preparing polymer-clay nanocomposite is explained thermodynamically. In the future, the study and development of polymer-clay nanocomposite is paid attention to the interfacial adhesion, clay dispersion within polymer, mechanism of clay intercalation or exfoliation.
Multilayer adsorptions and BET adsorption are analyzed statistical-mechanically. Which ensemble is selected for the analysis is unimportant, because each ensemble yields the same results. However, the amount of mathematical manipulations and the matter of convenience vary from ensemble to ensemble. Hence, multilayer adsorptions and BET adsorption are examined using a canonical and a grand canonical ensembles, and an ensemble of subsystems. Also, the characteristics of multilayer and BET adsorptions are delineated.
It is desirable to have an accurate expression on the temperature dependence of surface(or interfacial) tension Σ, because most of the interfacial thermodynamic functions can be derived from it. There have been proposed several equations on the temperature dependence of the surface tension, Σ(T). Among them Eotvos equation and the one modified by Katayama, which is called Katayama equation, for improving accuracies of Eotvos equation close to critical points, have been most well-known. In this article Katayama equation is interpreted on the basis of the cell model to understand the nature of the equation. The cell model results in an expression very similar to Katayama equation. This implies that, although Eotvos and Katayama equations were obtained on the basis of experimental results, they have a sound theoretical background. The Katayama equation is also modified with the phase volume replaced with a critical scaling expression. The modified Katayama equation becomes a power-law equation with the exponent slightly different from the value obtained by critical-scaling theory. This implies that Katayama equation can be replaced by a critical-scaling equation which is proven to be accurate.
Kelvin equation is revisited, which accounts for important phenomena observed frequently in nano-dispersion systems. They include vapor pressure increase for curved interfaces, nucleation, capillary condensation, Ostwald ripening and so on. The smaller the radius of curvature is, the more significant Kelvin equation becomes. Therefore, its meaning, curvature effect, and importance are examined and discussed.
The preparation of CaSO4 nanoparticle by vesicles formed spontaneously in cationic OTAC and anionic ADS mixed surfactant solution whose ratio is 0.3/0.7 is investigated. Added electrolytes for preparing nanoparticles reduce vesicle size about 200-300 nm comparing with that of pure vesicle whose size is 700-800 nm by DLS. The core of vesicles has 200 nm size and acts as nanoreactors which same size of monodisperse CaSO4 nanopaticles are formed. Although CaSO4 particles are formed at the outer of vesicles, they are very large and amorphous. The formed particles are identified with XRD analysis after separation due to coinciding with CaSO4 particles.
에멀젼 구조가 변하는 에멀젼 변환은 이미 40년 전에 알려졌다. 에멀젼 변환에서는 O/W 에멀젼이 W/O 에멀젼으로, 또는 이와 반대로 구조가 변하므로 연석상과 분산상이 서로 바뀌게 된다. 그러나 3상 에멀젼에서는 이와 같은 에멀젼 변환뿐만 아니라 어떤 특정한 온도에서 연속상은 변하지 않고 분산상의 구조가 바뀌는 현상이 관찰되었다. 이 현상을 에멀젼이라고 불렀으며 에멀젼 전이가 일어나는 온도를 에멀젼 전이 온도라고 하였다. 에멀젼 전이는 이론적인 고찰의 결과이었으며 양친매성 분자/기름/물의 두 3성분계에 대해서 실험적으로 관찰하였다. 이는 이제까지 보고되지 않았던 새로운 현상이다. 본 논문에서는 에멀젼 전이와 에멀젼 전이를 비교 분석하였다.
Self-diffusion coefficients of colloidal ass9Ciation structures in the aqueous solutions of anionic ammonium dodecyl sulfate (ADS) and cationic octadecyltrimethylammonium chloride (OTAC) surfactants were measured by pulsed-gradient spin echo NMR. The results were interpreted on the basis of the ADS/OTAC/water phase diagram. Crossing the phase boundaries, significant changes in self diffusion coefficients were observed and well correlated to the phase diagram. For the micelles their apparent radii were obtained from Stokes-Einstein equation. Their values were 15 for the ADS micelles and 54 a for the OTAC micelles, respectively. For vesicles which were formed spontaneously at different relative amounts of the surfactants and total surfactant concentrations, the radius was measured as 50 to 200 nm. This result is in fair agreement with those by TEM and light scattering.
The critical micelle concentration (CMC) at which micelles start to form from a surfactant solution is usually measured in terms of conventional concentration units. However, the thermodynamic potentials are expressed in terms of mole fraction XCMC and XCMC cannot be directly measured experimentally. The Gibbs free energy, δG*mic, in particular is related to XCMC through δG*mic = RTlnXCMC. When it comes to CMC, the molar CMC, CCMC, differs only by the proportionality C-1w with Cw being the molarity of water. Hence, CCMC is found to be a proper representation of CMC. However, in calculation of δG*mic and other thermodynamic potentials from the CMC, XCMC or CCMC/Cw should be used.
Sophorolipids were biosynthesized using a strain of yeast, Torulopsis bombicola ATCC22214. It has been reported that this yeast gives the highest yields for the production of biosurfactant sophorolipids. Hence, this yeast was used in this study. One of the objectives of this study is to increase the yield of the sophorolipid synthesis. To meet this end, basic culture medium was formulated on the basis of literature research to-date. When this medium was used, the increase in yield from 15% to 150% was observed compared to using the media in the literature. To examine how the interfacial characteristics of sophorolipids change with substrate, glucose (the first carbon source) was maintained in the media and after being cultured for three days, the second carbon sources such as alkanes, vegetable oils, alcohols or organic acids were added. The whole broth was extracted twice with ethyl acetate and the extract was analyzed by thin layer chromatograhy(TLC). After qualitative analyses by TLC, surface tensions of sophorolipids were measured by the Wilhelmy plate method and critical micelle concentration(CMC) was determined using these surface tension data. Also, interfacial tensions were measured by the spinning drop method and emulsions of the three-component water/decane/sophorolipid system were tested. Sophorolipids were effective and efficient in terms of surface tension reduction and CMC, but they were ineffective as emulsifiers because emulsions were separated within 30 minutes.
Excess enthalpies (HE) were measured by isothermal flow calorimetry for the nonionic amphiphile 2-butoxyethanol/water mixtures at 10 different temperatures (48.5 to 70℃) around and above the lower consolute solution temperature, Tlc. HE exhibits U-shape for the binary mixtures, and is large and negative which reflects substantial interaction between two chemical species. When the commonly used, semi-empirical Redlich-Kister (RK) polynomials were fitted to the measured HE, plots of HE vs. weight fraction provided more accurate fitting with fewer parameters than conventionally drawn HE vs. mole fraction plots. This was due to the enhanced symmetry of HE vs. weight fraction plots. Using the fitted Redlich-Kister polynomials and the Gibbs-Helmholtz relation, temperature dependence of the activity coefficients were found and compared to the values determined from vapor-liquid equilibria. The activity coefficients were in the range of one to three, indicating that the binary system deviates from ideality but not substantially. They slightly depended on temperature and the temperature effect was equivalent to 10 % change in the activity coefficients.
Surfactants are the surface-active molecules that display amphiphilicity, Because of this surface activity and amphiphilicity, surfactants have been used in wide industrial applications such as foods, detergents, cosmetics, medicine, polymers, paints, flotation, textiles. These days, their applications extend to high-technology industries such as microelectronics, magnetic recording material, advanced batteries, novel separations, etc. As new applications of surfactants are found and the demand of the surfactants increases, surfactant industry has been more pressed to face a formidable challenge, which is to develop surfactants that are envirionmentally friendly. In this regard biosurfactants may be alternatives to chemical surfactants, since biosurfactants are biologically compatible, more biodegradable, less toxic, and highly specific. Because of these excellent advantages over those of chemical surfactants, much efforts have been made in biosurfactant research. This article reviews biosurfactants in several aspects, that is, their definition, structures, properties, applications, and prospects.