Metallic thermodynamic stability

Marin, D. Mendicuti, F. Polarographic Determination of Composition and Thermodynamic Stability Constant of a Complex Metal Ion, /. Chem. Educ. 1988, 65, 916-918. 

The deposition of metals directly from these halides would require high temperatures to be efficient, but because of the thermodynamic stabilities of the hydrogen halides, direct reduction can readily be carried out with hydrogen at lower temperamres. The general reaction... 

Processes in which solids play a rate-determining role have as their principal kinetic factors the existence of chemical potential gradients, and diffusive mass and heat transfer in materials with rigid structures. The atomic structures of the phases involved in any process and their thermodynamic stabilities have important effects on drese properties, since they result from tire distribution of electrons and ions during tire process. In metallic phases it is the diffusive and thermal capacities of the ion cores which are prevalent, the electrons determining the thermal conduction, whereas it is the ionic charge and the valencies of tire species involved in iron-metallic systems which are important in the diffusive and the electronic behaviour of these solids, especially in the case of variable valency ions, while the ions determine the rate of heat conduction. 

A study of the lithium-ammonia reduction of 14-en-16-ones would extend our understanding of the configuration favored at C-14 in metal-ammonia reductions. Although several simple 14-en-16-ones are known, their reduction by lithium and ammonia apparently has not been described in the literature. Lithium-ammonia reduction of A-nortestosterone, a compound that structurally is somewhat analogous to a 14-en-16-one, affords roughly equal amounts of the 5a- and 5 -dihydro-A-nortestosterones. " This finding was interpreted as indicating that there is little difference in thermodynamic stability between the two stereoisomeric products. 

As with all determinations of thermodynamic stability, we comihehce by defining all stable phases possible, and their standard, chemical, potentials. For inost, metals there are many such phases, including oxides, hydroxides and dissolved ions. For brevity, here, only the minimum number of phases is Considered. The siriiplest system is a metal, ilf, which can oxidise lo form a stable dissolved pro,duct, (qorrpsipn), or to form a stable oxide MO (passivation), lit aqueous environments thfbe equilibria Can thereby be... 

The overall pattern of behaviour of titanium in aqueous environments is perhaps best understood by consideration of the electrochemical characteristics of the metal/oxide and oxide-electrolyte system. The thermodynamic stability of oxides is dependent upon the electrical potential between the metal and the solution and the pH (see Section 1.4). The Ti/HjO system has been considered by Pourbaix". The thermodynamic stability of an... 

The outstanding characteristics of the noble metals are their exceptional resistance to corrosive attack by a wide range of liquid and gaseous substances, and their stability at high temperatures under conditions where base metals would be rapidly oxidised. This resistance to chemical and oxidative attack arises principally from the Inherently high thermodynamic stability of the noble metals, but in aqueous media under oxidising or anodic conditions a very thin film of adsorbed oxygen or oxide may be formed which can contribute to their corrosion resistance. An exception to this rule, however, is the passivation of silver and silver alloys in hydrochloric or hydrobromic acids by the formation of relatively thick halide films. 

The factors leading to the high resistance of the noble metals to chemical attack, i.e. their thermodynamic stability over a wide range of conditions and the possibility of the formation of very thin protective films under oxidising conditions, have already been mentioned. A factor tending to reduce corrosion resistance in aqueous solutions is the tendency of these metals to form complexes with some anions. 

Fig. 7.77 Thermodynamic stability diagram for the Fe-Ni-Cr system at 1 143 K, assuming metal activities to be unity.-, phase boundaries involving Fe —phase boundaries involving Ni ----, phase boundaries involving Cr. The location of environments 1, 2, 3, and 4 are...

The thermodynamic stability of a species is a measure of the extent to which this species will be formed from other species under certain conditions, provided that the system is allowed to reach equilibrium. Consider a metal ion M in solution together with a monodentate ligand L, then the system may be described by the following stepwise equilibria, in which, for convenience, coordinated water molecules are not shown ... 

Cobalt is invariably present in commercial MHt battery electrodes. It tends to increase hydride thermodynamic stability and inhibit corrosion. However, it is also expensive and substantially increases battery costs thus, the substitution of Co by a lower/cost metal is desirable. Willems and Buschow [40] attributed reduced corrosion in LaNi 5 vCoi (x= 1 -5) to low Vn. Sakai et al. [47 J noted that LaNi25Co25 was the most durable of a number of substituted LaNi5 iCoi alloys but it also had the lowest storage capacity. 

Investigation of the configurational stability of allylmetals 2a, prepared by means of Rieke metals from geometrically pure l-chloro-2-decenes 1 a in THF, showed that the (Z)- and (ZT)-lithium, -sodium, and -potassium derivatives preserve the configuration of the precursors to a preparatively useful extent below — 90°C, — 50°C, and >0°C, respectively. For the pairs of 3,7-dimethyl-2,6-octadienyl derivatives (Z)- and ( )-2b, which differ less in their thermodynamic stability, the respective temperatures are — 60 °C, — 40 °C and >0°C124. 

Compared to the sum of covalent radii, metal-silicon single bonds are significantly shortened. This phenomenon is explained by a partial multiple bonding between the metal and silicon [62]. A comparison of several metal complexes throughout the periodic table shows that the largest effects occur with the heaviest metals. However, conclusions drawn concerning the thermodynamic stability of the respective M —Si bonds should be considered with some reservation [146], since in most cases the compared metals show neither the same coordination geometries nor the same oxidation states. 

It would be interesting to further examine the vaporization of Pu-intermetallics at higher temperatures in order to search for molecular vapor species involving Pu and the noble metals. Due to the directional nature of 5f electrons in Pu, they may not be involved in the bonding of the solid intermetallics, but could contribute to the stability of a gas phase molecule. Additional measurements of the thermodynamic stabilities of Np- and Am-noble metal intermetallics corresponding to the Pu phases considered in this work would also assist in establishing bonding trends. 

The thermodynamic stability of coordination compounds is relatively easy to determine, and provides us with a valuable pool of data from which we may assess the importance of ligand-field and other effects upon the overall properties of transition-metal compounds. The bulk of this chapter will be concerned with the thermodynamic stability of transition-metal compounds, but we will briefly consider kinetic factors at the close. 

In the introductory chapter we stated that the formation of chemical compounds with the metal ion in a variety of formal oxidation states is a characteristic of transition metals. We also saw in Chapter 8 how we may quantify the thermodynamic stability of a coordination compound in terms of the stability constant K. It is convenient to be able to assess the relative ease by which a metal is transformed from one oxidation state to another, and you will recall that the standard electrode potential, E , is a convenient measure of this. Remember that the standard free energy change for a reaction, AG , is related both to the equilibrium constant (Eq. 9.1)... 

Only two processes for the manufacture of Be are of industrial importance (i). the thermal reduction of BeF2 using Mg, and (ii) the electrolysis of BeCl2 in a molten chloride electrolyte. Direct reduction of the oxide is ineffective because of its thermodynamic stability only Ca reduces BeO to the metal unfortunately, Ca cannot be used since it forms a stable intermetallic compound with Be, BejjCa. 

The areas bounded by solid lines correspond to regions of thermodynamic stability of certain substances that are named in the diagram. This stability is relative. The dashed line a in the diagram corresponds to the equilibrium potential of the hydrogen electrode. Metallic zinc, for which the reaction lines are below the line for the hydrogen electrode, can be oxidized while hydrogen is evolved (see Section 2.4.1). 

The chelate ring size principle can have structural effects as well as effects on thermodynamic stability in aqueous solution. An example is coordination of metal ions by sugars (44). The cyclic polyol cts-inositol can coordinate metal ions in two distinct ways (Fig. 14) (45). In ax-ax-ax bonding (Fig. 14), the metal ion is part of three fused six-membered chelate rings. Alternatively, in ax-eq-ax coordination, the metal ion is part of two fused five-membered and one six-membered chelate rings. Angyal has noted that metal ions of radius more than 0.8 A adopt the ax-eq-ax structure (44), whereas with an ionic radius... 

In the past few years, a large number of experimental and theoretical studies have focused on metal oxide surfaces with the aim of gaining insight into their catalytic, photocatalytic, and gas-sensing activity [68]. Owing to its thermodynamic stability and relatively easy preparation, the rutile Ti02(l 10) surface has evolved into one of the key models for metal oxide surfaces. For example, it has been extensively used in the research of biocompatible materials, gas sensors, and photocatalysts [69]. 

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