Application of programmed thermodesorption of the liquid under quasi-isothermal conditions to investigate physicochemical properties of liquid layers and solid surfaces

This paper presents the results of measurements of the programmed thermodesorption of polar and nonpolar liquids from the surface of different types of solids. The course of thermodesoption was found to depend on the properties of the solid and the wetting liquid. Thermodesorption occurred not exponentially but in steps, which reflects the noncontinuous changes in the properties of the surface layer with the distance from the solid surface. This effect intensified with the increase in polarity of the wetting liquid and the heterogeneity of the solid surface. The earlier investigations showed that application of the method of differential thermal analysis allowed determination of the distribution of the adsorption potential of the liquid on the solid surface.The author is indebted to Prof. M. Jaroniec for very fruitful discussions and to Prof. J. Choma for the activated carbon samples.     

Characterization of macromolecules in liquid solutions by thermal diffusion. I. Dependence of the soret coefficient on the nature of the dispersing medium

Experiments have been carried out on thermal diffusion of macromolecular particles dispersed in various liquids, with the object of checking some predictions of the radiation-pressure theory of Soret effect in liquids and of establishing a method of physical characterization of macromolecules in liquid solutions. The experimental results confirm the importance of the ratio G between thermal conductivity K and (phase) velocity v of high-frequency elastic waves of the materials composing the mixture in determining the thermodiffusive behavior of a liquid solution. We have shown that the migration of the macromolecular component takes place in the same direction in which thermal energy is flowing or opposite to it, depending on whether G of the dispersed particles is smaller or larger relative to the G of the liquid. Another aspect of the same phenomenon may be observed when macroscopic pieces of nonmetallic materials are suspended in a liquid, and heat is made to flow through this solid plunger and the surrounding liquid. The experiments performed with molecular solutions and with macroscopic plungers mutually complement and confirm each other. Anomalous results obtained in the case of solutions of polyvinylpyrrolidone in methanol are also discussed, and the possibility that this might be the consequence of the existence of a marked velocity dispersion in the high-frequency region of the spectrum of thermal waves in both water and methyl alcohol is indicated. Finally the possibility is hinted that thermal diffusion might have been responsible for the phenomena of molecular selection and evolution which ultimately led to the origin of life on our planet.     

On Neglecting the Polar Nature of Halogenated Hydrocarbons in the Surface Energy Determination of Polar Solids from Contact Angle Measurements

The generally accepted strategy of neglecting the polar nature of halogenated liquids in the surface energy determination using the Lifshitz-van der Waals/Lewis acid-base (LW/AB) approach may lead to erroneous and inconsistent results for polar solids. This was demonstrated in a simulation study carried out on monopolar basic surfaces using water, glycerol, and hypothetical liquids whose surface energy characteristics (gamma(L)(LW)=50 mJ/m(2), gamma(L)(-)=0, and gamma(L)(+)=0-1 mJ/m(2)) were chosen to approximate halogenated hydrocarbons. Neglect of the liquid polarity overestimates the LW component and underestimates the basic parameter of the solid surface energy. This effect increases rapidly with an increase in the actual (nonzero) gamma(L)(+) value of supposedly apolar liquid. Consequently, results with an appropriate level of precision can be obtained only with liquids having gamma(L)(+)<0.02 mJ/m(2). For liquids having gamma(L)(+) approximately 0.5 mJ/m(2) (diiodomethane, s-tetrabromoethane, and, probably, other halogenated hydrocarbons), neglect of the liquid polarity causes errors up to 15% in the LW component and up to 100% in the basic parameter of the solid surface energy. The quantitative trends established in the simulation study were indeed observed in an experimental study performed on the surfaces of poly(methyl methacrylate) and polystyrene using water, glycerol, and diiodomethane or s-tetrabromoethane as the test liquids. Copyright 2000 Academic Press.     

To the thermodynamics of saturation of liquids with inert gases

In continuation of the earlier advanced point of view concerning the non-true character of solutions of inert gases in liquids, a thermodynamic analysis of the transfer of particles of these gases to the liquid at constant temperature and sum of volumes of coexisting phases was performed. The analysis is based on the linearity of the concentration dependences of the enthalpy and entropy of noble gases and nitrogen and approximation of the real process by the hypothetical one including two stages: transfer of some number of moles of the gas from the intrinsic phase to the physical microvolume numerically equal to the volume of the intermolecular space of the liquid accessible for gas particles and the distribution of these particles over particular cavities of the latter. The contact of inert gases with liquids results in the formation of a thermodynamically unstable two-phase binary system, whose liquid phase can be considered as internally strained dispersion of gas clusters.     

Determination of contact angles on microporous particles using the thin-layer wicking technique

The properties of particle-stabilized emulsions, especially with regard to phase inversion, are very dependent on the contact angle that the particles experience at the oil-water interface. For the very small particles used for such emulsions (often a few tens of nm), it is impossible to measure this contact angle directly. Its value could be calculated if it were possible to determine the components of the solid surface free energy. To establish a method suitable for such particles, we have investigated the imbibition of five probe liquids into a porous bed of silica (commercial TLC plates) using the thin-layer wicking technique. For all liquids, the difference between wicking rate for bare plates and for those pre-contacted with the vapors is large but it is not due to an advancing angle effect on bare plates. Our analysis shows that it is due to the diversion of flowing liquid into blind pores which are already filled in the pre-contacted case. Thus a new model is proposed describing wicking in a porous medium with very small blind pores by introducing a parameter into the Washburn equation that corrects for this capillary condensation effect. The parameter needed is determined independently using gravimetric adsorption measurements. When this modified Washburn equation is used, the difference between advancing and receding contact angle is actually quite small. When the averages are used as the Young's contact angles, values for the surface energy components of silica are obtained that are completely consistent between the five liquids and have magnitudes expected for this type of silica surface.     

The extent of molecular orientation at liquid/vapor interface of pyridine and its alkyl derivatives by molecular dynamics simulation

In this paper, molecular dynamics simulation was performed to investigate the liquid∕vapor interfacial structure of neat polar liquids. Large-scale ensembles of liquid pyridine and its alkyl derivatives, 4-methylpyridine and 4-ethylpyridine, were simulated by classical molecular dynamics at 298 K. For the liquid system of low polarity, the surface density profile of the atoms meet exactly at the middle of interfacial region, and atoms of hydrophobic nature can be hardly discriminated from hydrophilic ones in either vapor or liquid sides. For a liquid system of high polarity, the density profile of atoms with different nature is highly discriminated all over the interfacial region, and as the polarity increases, a dense region of atomic density is clearly developed in the subsurface region. The recognized bivariate method was also used to study the molecular orientational distribution quantitatively. Orientational analysis of the three liquid systems indicates that the pyridine ring plane in the outmost surface tends to be vertical. Its tendency in the innermost interfacial region is parallel. The orientational states available to 4-ethylpyridine and pyridine are discriminated by predicting the possibility of a bisector-wise tumbling for the ring plane in pyridine and a side-wise tumbling in 4-ethylpyridine. The orientational distribution maps explain the trend of experimental surface tension and surface entropy. As the dipole moment of these liquids increases with the alkyl chain length, the surface structural profile changes from a regular definite one to a surface of complex atomic structure involving a dense phase near the interface. The development of dense region in alkyl derivatives is the result of segregation of molecules due to the alkyl group, which is captured and discriminated by molecular dynamics simulation even when the length of a short alkyl chain is increased by one carbon atom.     

The selectivity of the stationary liquid in vapour phase chromatography

Vapour phase chromatography is a highly efficient analytical technique for the separation of gases and volatile liquids. The stationary phase in this percolation process is a liquid supported by an inert solid carrier material of a suitable particle size. The important role played by this liquid in the separation of a mixture into its components is discussed.     

Surface Modification and Contact Interaction of Particles

Abstract

The effects of particle surface modification by ambient media and surfactant adsorption on the cohesive forces in the immediate contacts between individual particles have been studied with the CF (cohesive force) apparatus. The values of the free energy of interaction in direct coagulation contacts between particles of various types in liquids of different polarity and in the presence of various surfactants have been measured. They cover a broad range of several orders of magnitude; these interactions define the rheological properties of concentrated thixotropic systems and their stability with respect to peptization. A similar experimental technique has been used for studying active media influences on various physico‐chemical processes of particle bridging and formation of the phase contacts responsible for the mechanical properties of related solid structures and their resistance to fracture. The effect of the adsorption induced decrease in strength and durability of such porous structures with phase contacts and compact solids is considered.     

Effect of electrical potential on the electro-demulsification of oily sludge

Oily sludge, produced mostly in petroleum refineries and petrochemical industries, is one of the major industrial wastes that require treatment. Typically, these sludge wastes are water-in-oil emulsions that are stabilized by fine solids. These fine particles adsorb at the droplet surface and by lowering the demulsification rate constant, act as a barrier to prevent droplet coalescence. In this investigation, the effects of different electrical potential gradients and amphoteric surfactant on effectiveness of phase separation were investigated. It was concluded that lower electrical potential (0.5 V/cm) produced a higher demulsification rate. The solid phase remaining after the experiment was of a more compact and stable consistency. It was concluded that application of the amphoteric surfactant does not improve the total efficiency of the process. The role of oil constituents in stabilizing water-in-oil emulsions, and their effect on the dynamics of the process, were considered in every step of the experiment. Analysis of pH changes, resistance evolution, and hydrocarbon polarity analysis confirmed that the application of lower electrical gradient results in better phase separation.     

Kinetics of molecular motions in liquids and its correlation with kinetics of radical liquid–phase reactions

Stable nitroxide radicals and ESR techniques have been used to investigate rotational and translational motions of molecules in the liquid state. It is found that for hydrocarbons and molecules with low polarity the rotational frequencies are about an order of magnitude faster than translational encounters. Arrhenius parameters are reported for the rates of both types of processes. A scheme is given for the relation of these motions to radical recombination in solution and also to reactions requiring activation energy. The consequences of this scheme are examined. Such important properties as hydrodynamic fluidity, thermal conductivity, processes of extraction and solution, occurring in the liquid phase as well as at the interface are determined by mobility of particles in the liquid. The problem of molecular mobility is of essential significance for the kinetics of chemical and chemico-physical processes in the liquid phase. Application of both ESR techniques and stable nitroxide radicals for kinetic studies of molecular motions in liquids and the correlation between molecular mobility and the kinetic parameters of liquid-phase radical reactions have been studied in the present paper.     

Solid-liquid phase transition of tin particles observed by UHV high resolution transmission electron microscopy: pseudo-crystalline phase

Solid-liquid transition of fine tin particles having diameter of 2–10 nm is studied in-situ by high-resolution transmission electron microscopy under a ultra-high vacuum condition. Melting temperature is confirmed to decrease with the decrease of particle diameter. The particles less than the critical size, 2r _c?5 nm, are found to have a specific phase between the solid and the liquid phase. The particle in this “pseudo-crystalline” phase contains crystalline embryos in it. Particles larger than the critical size have sharp liquid-solid transition, which completed within the time resolution of our microscope observation, 33 ms upon heating or cooling process. Large solid particles have Wulff's polyhedron, while particles around the critical diameter have rather spherical shape. Structural anomaly at the critical size occurs all over the outer most surface layer slightly below the melting temperature. Origin of the “pseudo-crystalline” phase and surface pre-melting phenomena are discussed.     

In situ liquid SIMS analysis of uranium oxide

Trace analysis of nuclear materials in solid particles collected in the environment or particles in liquid slurry generated in nuclear material manufacturing processes can pinpoint elemental, organic, and isotopic signatures of nuclear fuel cycle activities and processes. Such information can support nuclear safeguards programs by increasing our ability to detect undeclared nuclear materials, routine activities for safeguarding at declared facilities, and illicit activities. However, trace radioactive material analysis in liquids and slurries is challenging using bulk approaches. For example, one drawback of sensitive analysis such as inductively coupled plasma mass spectrometry (ICP-MS) is that sample is consumed or destroyed as a result of the technical approach. We developed a vacuum compatible microfluidic interface to enable surface analysis of liquids and solid–liquid interactions using time-of-flight secondary ion mass spectrometry (ToF-SIMS). In this work, we illustrate the initial results from the analysis of liquid uranium oxide standard solutions using in situ liquid SIMS. Because the liquid SIMS analysis is almost nondestructive, the same sample can then be analyzed by other analytical techniques or saved for future reference. Consequently, multimodal analysis is possible. Our results demonstrate that in situ liquid SIMS can be used as a new approach to analyze radioactive materials in liquid and slurry forms of relevance to diverse applications.     

Modifying the liquid/liquid interface: pores, particles and deposition

The modification of the liquid/liquid interface with solid phases is discussed in this article. Modified interfaces can be formed with molecular assemblies, but here attention is focussed on solid materials such as mesoscopic particles, or microporous and mesoporous membranes. Charge transfer across the modified liquid/liquid interface is considered in particular. The most obvious consequence of the introduction of such modifying components is their effect on the transport to, and the transfer of material across, the liquid/liquid interface, as measured voltammetrically for example. One particularly interesting reaction is interfacial metal deposition, which can also be studied under electrochemical control: the initial formation of metal nuclei at the interface transforms it from the bare, pristine state to a modified state with very different reactivity. Deposition at interfaces between liquids is compared and contrasted with the cases of metal deposition in bulk solution and conventional heterogeneous deposition on conducting solid surfaces. Comparison is also made with work on the assembly of pre-formed micron and nanometre scale solids at the liquid/liquid interface.     

Novel method for in-situ surfactant-based solid-phase extraction: application to the determination of Co(II) and Ni(II) in aqueous samples

We report on a completely new kind of solid phase extraction which we term in-situ surfactant-based solid-phase extraction (ISS-SPE). It represents a simple and rapid method for extraction from aqueous samples and preconcentration of compounds containing hydrophobic (alkyl) groups. A cationic surfactant containing alkyl chain is dissolved in the aqueous sample. Following the addition of hexafluorophosphate (HFP; an ion-pairing anion), solutions turn cloudy due to the interaction between the surfactant and the HFP ion. This is due to the formation of fine solid particles composed of the HFP salt of the cationic surfactant. The alkyl groups of the surfactant in the solid particles strongly interact with hydrophobic groups of analytes and become bound. The solid particles are centrifuged, and the sedimented particles can be either dissolved in an appropriate organic solvent, or leached with a solvent to recover the absorbed analyte(s). The method presented here has distinct advantages in that the extraction times are short and recoveries are high, probably a result of the formation of very fine particles of large specific surface, and of their good dispersion in the sample solution. The performance of ISS-SPE was demonstrated by extracting chelates of Co(II) and Ni(II) from water samples. Under the optimized conditions, the preconcentration factors are 51 and 45, respectively, and the detection limits are 0.9 and 0.6???g?L^?1. The method was validated by the analysis of a certified reference material and by comparing results with those obtained by electrothermal AAS.

Foams from non-aqueous systems

The multi-phase approach to clarify the fundamentals of the stability of foams from non-aqueous liquids has been further developed. The two-phase liquid/liquid crystal line of attack for the liquid oil variety has been extended to foams stabilized by solid particles, in turn leading to progress in the fundamental science of solid metal foams and plastic foams.     

Evaluation of the silanol-suppressing potency of ionic liquids

Recently, increasing attention has been paid to the use of ionic liquids for high-performance liquid chromatography (HPLC) and capillary electrophoresis. In the present study, the silanol-suppressing potency of ionic liquids was evaluated by HPLC using the two-retention site model proposed previously by Nahum and Horváth (J. Chromatogr. 1981, 203, 53-63). The binding constant, KA, in that approach has been demonstrated to reliably reflect the ability of the ionic liquids to block the silanols of the silica support material of the stationary phase. The determinations were carried out for ionic liquids of the 1-alkyl-3-methylimidazolium group with the use of a series of basic drugs as the test analytes. Comparison of ionic liquids with standard mobile phase additives such as triethylamine showed the former to possess advantages as silanol suppressors in HPLC. The main advantage of the method is that it provides a simple and fast determination of the silanol complex stability, which allowed comparison of the suppressing efficiency of several ionic liquids.     

Liquid-liquid phase transformations and the shape of the melting curve

The phase diagram of elemental liquids has been found to be surprisingly rich, including variations in the melting curve and transitions in the liquid phase. The effect of these transitions in the liquid state on the shape of the melting curve is analyzed. First-order phase transitions intersecting the melting curve imply piecewise continuous melting curves, with solid-solid transitions generating upward kinks or minima and liquid-liquid transitions generating downward kinks or maxima. For liquid-liquid phase transitions proposed for carbon, phosphorous selenium, and possibly nitrogen, we find that the melting curve exhibits a kink. Continuous transitions imply smooth extrema in the melting curve, the curvature of which is described by an exact thermodynamic relation. This expression indicates that a minimum in the melting curve requires the solid compressibility to be greater than that of the liquid, a very unusual situation. This relation is employed to predict the loci of smooth maxima at negative pressures for liquids with anomalous melting curves. The relation between the location of the melting curve maximum and the two-state model of continuous liquid-liquid transitions is discussed and illustrated by the case of tellurium.     

H2 formation from the radiolysis of liquid water with zirconia

The formation of H(2) in the radiolysis of liquid water containing nanometer sized ZrO(2) particles was found to be dependent on the crystalline structure of the particle. Zirconia particles of a few tens of nanometer diameter may be formed with the tetragonal crystalline structure at room-temperature rather than the more stable monoclinic form for bulk zirconia. Radiolysis of liquid water containing tetragonal ZrO(2) particles exhibits a significant increase in the decomposition of water to H(2) compared to the monoclinic form. Annealing the tetragonal particles to the monoclinic structure results in the loss of excess H(2) production above that found with water alone. The results show that surface morphology is extremely important in the decomposition of liquids at solid interfaces, which may have many consequences ranging from nuclear waste storage to the H(2) economy.     

Magnetic Actuation of Drops and Liquid Marbles Using a Deformable Paramagnetic Liquid Substrate

The magnetic actuation of deposited drops has mainly relied on volume forces exerted on the liquid to be transported, which is poorly efficient with conventional diamagnetic liquids such as water and oil, unless magnetosensitive particles are added. Herein, we describe a new and additive‐free way to magnetically control the motion of discrete liquid entities. Our strategy consists of using a paramagnetic liquid as a deformable substrate to direct, using a magnet, the motion of various floating liquid entities, ranging from naked drops to liquid marbles. A broad variety of liquids, including diamagnetic (water, oil) and nonmagnetic ones, can be efficiently transported using the moderate magnetic field (ca. 50 mT) produced by a small permanent magnet. Complex trajectories can be achieved in a reliable manner and multiplexing potential is demonstrated through on‐demand drop fusion. Our paramagnetofluidic method advantageously works without any complex equipment or electric power, in phase with the necessary development of robust and low‐cost analytical and diagnostic fluidic devices.