Liquid molecular alloys

Ballesteros, B., Coco, S. and Espinet, P. (2004) Mesomorphic Mixtures of Metal Isocyanide Complexes, Induding Smectic C Mesophases at room temperature and Liquid Crystalline Molecular Alloys . Chemistry of Materials, 16, 2062-2067. 

Equation (4.70) is a starting point in the determination of diffusivities in liquid metal alloys, but in most real systems, experimental values are difficult to obtain to confirm theoretical expressions, and pair potentials and molecular interactions that exist in liquid alloys are not sufficiently quantified. Even semiempirical approaches do not fare well when applied to liquid alloy systems. There have been some attempts to correlate diffusivities with thermodynamic quantities such as partial molar enthalpy and free energy of solution, but their application has been limited to only a few systems. 

AB INITIO MOLECULAR DYNAMICS SIMULATIONS OF LIQUID ALLOYS ... 

Another characteristic point is the special attention that in intermetallic science, as in several fields of chemistry, needs to be dedicated to the structural aspects and to the description of the phases. The structure of intermetallic alloys in their different states, liquid, amorphous (glassy), quasi-crystalline and fully, three-dimensionally (3D) periodic crystalline are closely related to the different properties shown by these substances. Two chapters are therefore dedicated to selected aspects of intermetallic structural chemistry. Particular attention is dedicated to the solid state, in which a very large variety of properties and structures can be found. Solid intermetallic phases, generally non-molecular by nature, are characterized by their 3D crystal (or quasicrystal) structure. A great many crystal structures (often complex or very complex) have been elucidated, and intermetallic crystallochemistry is a fundamental topic of reference. A great number of papers have been published containing results obtained by powder and single crystal X-ray diffractometry and by neutron and electron diffraction methods. A characteristic nomenclature and several symbols and representations have been developed for the description, classification and identification of these phases. 

When it is necessary to dismantle a vacuum line, as much care is needed as during its construction, but the considerations are different. This is because the well-used line will probably have attached to it various reservoirs of solvents and liquid reagents and containers with drying agents (Na Alms, liquid Na + K alloy, molecular sieves, etc.), and there will be condensers... 

In solution, block copolymers display interesting colloidal and interfacial properties. They can be used as emulsifying agents in water-oil and oil-oil systems (6 ). In the later case, the oil phases are solid and they give rise to polymeric alloys (7.) or they are liquid and they allow the preparation of latexes in organic medium (8 ). However, the molecular structure of block copolymers based on polybutadiene PB (70 ) and polystyrene PS behave as thermoplastic elastomers when engaged in multiblock (PB-PS)n or triblock (PS-PB-PS) structures but never when implied in inverse triblock or diblock arrangements. Similarly the... 

The sodium-potassium alloy (45-90 weight %K) is molten at room temperature and cesium melts at 28.5°, so both of these are easily handled as liquids. For example, a hypodermic syringe is convenient for their transfer. The sodium-potassium alloy is made by heating the two metals together while they are protected by a high-molecular-weight hydrocarbon. 

Subject areas for the Series include solutions of electrolytes, liquid mixtures, chemical equilibria in solution, acid-base equilibria, vapour-liquid equilibria, liquid-liquid equilibria, solid-liquid equilibria, equilibria in analytical chemistry, dissolution of gases in liquids, dissolution and precipitation, solubility in cryogenic solvents, molten salt systems, solubility measurement techniques, solid solutions, reactions within the solid phase, ion transport reactions away from the interface (i.e. in homogeneous, bulk systems), liquid crystalline systems, solutions of macrocyclic compounds (including macrocyclic electrolytes), polymer systems, molecular dynamic simulations, structural chemistry of liquids and solutions, predictive techniques for properties of solutions, complex and multi-component solutions applications, of solution chemistry to materials and metallurgy (oxide solutions, alloys, mattes etc.), medical aspects of solubility, and environmental issues involving solution phenomena and homogeneous component phenomena. 

Ehrenfest s concept of the discontinuities at the transition point was that the discontinuities were finite, similar to the discontinuities in the entropy and volume for first-order transitions. Only one second-order transition, that of superconductors in zero magnetic field, has been found which is of this type. The others, such as the transition between liquid helium-I and liquid helium-II, the Curie point, the order-disorder transition in some alloys, and transition in certain crystals due to rotational phenomena all have discontinuities that are large and may be infinite. Such discontinuities are particularly evident in the behavior of the heat capacity at constant pressure in the region of the transition temperature. The curve of the heat capacity as a function of the temperature has the general form of the Greek letter lambda and, hence, the points are called lambda points. Except for liquid helium, the effect of pressure on the transition temperature is very small. The behavior of systems at these second-order transitions is not completely known, and further thermodynamic treatment must be based on molecular and statistical concepts. These concepts are beyond the scope of this book, and no further discussion of second-order transitions is given. 

Considerable evidence exits of the survival of Zintl ions in the liquid alloy. Neutron diffraction measurements [5], as well as molecular dynamics simulations [6, 7], give structure factors and radial distribution functions in agreement with the existence of a superstructure which has many features in common with a disordered network of tetrahedra. Resistivity plots against Pb concentration [8] show sharp maxima at 50% Pb in K-Pb, Rb-Pb and Cs-Pb. However, for Li-Pb and Na-Pb the maximum occurs at 20% Pb, and an additional shoulder appears at 50% Pb for Na-Pb. This means that Zintl ion formation is a well-established process in the K, Rb and Cs cases, whereas in the Li-Pb liquid alloy only Li4Pb units (octet complex) seem to be formed. The Na-Pb alloy is then a transition case, showing coexistence of Na4Pb clusters and (Pb4)4- ions and the predominance of each one of them near the appropiate stoichiometric composition. Measurements of other physical properties like density, specific heat, and thermodynamic stability show similar features (peaks) as a function of composition, and support also the change of stoichiometry from the octet complex to the Zintl clusters between Li-Pb and K-Pb [8]. 

In this work we study a number of isolated clusters which may be relevant for understanding the clustering in the liquid alloys. Of course, the behaviour of those clusters in the alloy may be more complicated due to the interaction with the condensed medium, but by studying free clusters we expect to obtain useful information about the tendency of the atoms to cluster in the alloy. A preliminary calculation [9] using the Density Functional Formalism (DFT) [10, 11] and a simplified model for the cluster structure [12] has confirmed the high stability of the A4Pb and A4Pb4 species (with A = Li, Na, K, Rb, Cs). However, the drastic simplification of the cluster structure used in that model calls for more accurate calculations. Consequently, in this work we report the results of ab initio molecular-dynamics DFT calculations. 

Over the past two decades, ionic liquids (ILs) have attracted considerable interest as media for a wide range of applications. For electrochemical applications they exhibit several advantages over the conventional molecular solvents and high temperature molten salts they show good electrical conductivity, wide electrochemical windows of up to 6 V, low vapor pressure, non-flammability in most cases, and thermal windows of 300-400 °C (see Chapter 4). Moreover, ionic liquids are, in most cases, aprotic so that the complications associated with hydrogen evolution that occur in aqueous baths are eliminated. Thus ILs are suitable for the electrodeposition of metals and alloys, especially those that are difficult to prepare in an aqueous bath. Several reviews on the electrodeposition of metals and alloys in ILs have already been published [1-4], A selection of published examples of the electrodeposition of alloys from ionic liquids is listed in Table 5.1 [5-40]. Ionic liquids can be classified into water/air sensitive and water/air stable ones (see Chapter 3). Historically, the water-sensitive chloroaluminate first generation ILs are the most intensively studied. However, in future the focus will rather be on air- and water-stable ionic liquids due to their variety and the less strict conditions under which... 

Means other than pressurized gas or cryogenic liquid theoretically exist for useful transportation and storage of molecular hydrogen. They principally include pressurized absorption in metallic alloys and on or in carbon or other... 

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