Intercalation thermodynamics

In the thermodynamic study of duplex formation, a variety of complementary pairs of relatively simple, well-defined oligonucleotides are employed, " while the intercalation thermodynamics was examined with more complex or natural DNA duplexes. " Typical intercalating agents examined are acridine orange, acriflabine, actinomycin, daunomycin, ethidium bro-... 

The simplest way to approach the intercalation thermodynamics based on the lattice gas model is to assume that the intercalated ions do not interact with one another, that the available sites are equivalent and occupied by the ions at random, and that the chemical potential of electrons are constant. The entropy of distributing ions randomly on a fraction 8 of the available sites (N) in the intercalation compounds is... 

The simple models of intercalation thermodynamics have been found adequate for lithium intercalation in LixMogScg [65], lithium intercalation in Li,TiS2 [66] and CIOJ intercalation in poly(Os(bpy)2(vpy)2) [67]. The... 

Apart from the work toward practical lithium batteries, two new areas of theoretical electrochemistry research were initiated in this context. The first is the mechanism of passivation of highly active metals (such as lithium) in solutions involving organic solvents and strong inorganic oxidizers (such as thionyl chloride). The creation of lithium power sources has only been possible because of the specific character of lithium passivation. The second area is the thermodynamics, mechanism, and kinetics of electrochemical incorporation (intercalation and deintercalation) of various ions into matrix structures of various solid compounds. In most lithium power sources, such processes occur at the positive electrode, but in some of them they occur at the negative electrode as well. 

The intercalation compounds of lithium with graphite are very different in their behavior from intercalation compounds with oxides or halcogenides. Intercalation processes in the former compounds occur in the potential region from 0 to 0.4 V vs. the potential of the lithium electrode. Thus, the thermodynamic activity of lithium in these compounds is close to that for metallic lithium. For this reason, lithium intercalation compounds of graphite can be used as negative electrodes in batteries rather than the difficultly of handling metallic lithium, which is difficult to handle. 

At present, intercalation compounds are used widely in various electrochemical devices (batteries, fuel cells, electrochromic devices, etc.). At the same time, many fundamental problems in this field do not yet have an explanation (e.g., the influence of ion solvation, the influence of defects in the host structure and/or in the host stoichiometry on the kinetic and thermodynamic properties of intercalation compounds). Optimization of the host stoichiometry of high-voltage intercalation compounds into oxide host materials is of prime importance for their practical application. Intercalation processes into organic polymer host materials are discussed in Chapter 26. 

The electrochemical intercalation/insertion is not a special property of graphite. It is apparent also with many other host/guest pairs, provided that the host lattice is a thermodynamically or kinetically stable system of interconnected vacant lattice sites for transport and location of guest species. Particularly useful are host lattices of inorganic oxides and sulphides with layer or chain-type structures. Figure 5.30 presents an example of the cathodic insertion of Li+ into the TiS2 host lattice, which is practically important in lithium batteries. 

In order to understand the thermodynamic issues associated with the nanocomposite formation, Vaia et al. have applied the mean-field statistical lattice model and found that conclusions based on the mean field theory agreed nicely with the experimental results [12,13]. The entropy loss associated with confinement of a polymer melt is not prohibited to nanocomposite formation because an entropy gain associated with the layer separation balances the entropy loss of polymer intercalation, resulting in a net entropy change near to zero. Thus, from the theoretical model, the outcome of nanocomposite formation via polymer melt intercalation depends on energetic factors, which may be determined from the surface energies of the polymer and OMLF. 

Biver, T., De Biasi, A., Secco, E, Venturing M., and Yarmoluk, S. (2005) Cyanine dyes as intercalating agents Kinetic and thermodynamic studies on the DNA/Cyan40 and DNA/CCyan2 systems. Biophys. J. 89, 374-383. 

The value of the thermodynamic property in question is the difference in values for the clay-water sample and the same measurement on an equivalent amount of pure, anhydrous clay (6.). This procedure involves two assumptions 1) the added water is uniformly adsorbed on all clay layers, and 2) the thermodynamic properties of the clay itself do not change when the clay expands and is intercalated by water molecules. 

Compounds made by insertion at room temperature are often metastable - if heated, they change their structure or decompose into other compounds. That does not rule out using thermodynamics it just means that processes happening slowly compared to the duration of an experiment are assumed to be frozen. At room temperature, the ratio of Mo to Se in a host like Mo Seg is fixed. From the point of view of thermodynamics, the constraint that the host remain Mo Seg means that we can regard an intercalation compound like Li -MogSeg as a pseudo-binary compound instead of a ternary one. 

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