Thermodynamic instability

Indoles can also be alkylated by lactones[l4]. Base-catalysed reactions have been reported for (3-propiolactone[15], y-butyrolactone[10] and 5-valerolac-tone[10]. These reactions probably reflect the thermodynamic instability of the N -acylindole intermediate which would be formed by attack at the carbonyl group relative to reclosure to the lactone. The reversibility of the JV-acylation would permit the thermodynamically favourable N-alkylation to occur. 

The coordination chemistry of NO is often compared to that of CO but, whereas carbonyls are frequently prepared by reactions involving CO at high pressures and temperatures, this route is less viable for nitrosyls because of the thermodynamic instability of NO and its propensity to disproportionate or decompose under such conditions (p. 446). Nitrosyl complexes can sometimes be made by transformations involving pre-existing NO complexes, e.g. by ligand replacement, oxidative addition, reductive elimination or condensation reactions (reductive, thermal or photolytic). Typical examples are ... 

Anhydrous NaC102 crystallizes from aqueous solutions above 37.4° but below this temperature the trihydrate is obtained. The commercial product contains about 80% NaC102. The anhydrous salt forms colourless deliquescent crystals which decompose when heated to 175-200° the reaction is predominantly a disproportionation to C103 and Cl but about 5% of molecular O2 is also released (based on the C102 consumed). Neutral and alkaline aqueous solutions of NaC102 are stable at room temperature (despite their thermodynamic instability towards disproportionation as evidenced by the reduction potentials on p. 854). This is a kinetic activation-energy effect and, when the solutions are heated near to boiling, slow disproportionation occurs ... 

All the anhydrous - -3 and +2 halides of iron are readily obtained, except for iron(III) iodide, where the oxidizing properties of Fe and the reducing properties of 1 lead to thermodynamic instability. It has, however, been prepared in mg quantities by the following reaction, with air and moisture rigorously excluded,... 

Although corrosion is due to the thermodynamic instability of a metal in a specific environment, and although in many metal/environment systems attack will tend to be uniform, there are a variety of factors associated with the metal, the environment and the geometry of the system that may result in the attack being localised. 

Metals immersed or partly immersed in water tend to corrode because of their thermodynamic instability. Natural waters contain dissolved solids and gases and sometimes colloidal or suspended matter all these may affect the corrosive projjerties of the water in relation to the metals with which it is in contact. The effect may be either one of stimulation or one of suppression, and it may affect either the cathodic or the anodic reaction more rarely there may be a general blanketing effect. Some metals form a natural protective film in water and the corrosiveness of the water to these metals depends on whether or not the dissolved materials it contains assist in the maintenance of a self-healing film. 

The potential for electrochemical corrosion in a boiler results from an inherent thermodynamic instability, with the most common corrosion processes occurring at the boiler metal surface and the metal-BW interface (Helmholtz double layer). These processes may be controlled relatively easily in smaller and simpler design boilers (such as dual-temperature, LPHW heating, and LP steam boiler systems) by the use of various anodic inhibitors. 

H2O departs about 10 times as fast as CN . A good attacking group is a poor leaving group with very few exceptions. OH is notable, for it is a very poor nucleophile for Pt(II) but is only very slowly replaced. In the main, lability also corresponds to thermodynamic instability, for example in the series... 

These two examples show that regular patterns can evolve but, by definition, dissipative structures disappear once the thermodynamic equilibrium has been reached. When one wants to use dissipative structures for patterning of materials, the dissipative structure has to be fixed. Then, even though the thermodynamic instability that led to and supported the pattern has ceased, the structure would remain. Here, polymers play an important role. Since many polymers are amorphous, there is the possibility to freeze temporal patterns. Furthermore, polymer solutions are nonlinear with respect to viscosity and thus strong effects are expected to be seen in evaporating polymer solutions. Since a macromolecule is a nanoscale object, conformational entropy will also play a role in nanoscale ordered structures of polymers. 

Thermodynamic instability of human 6 light chains correlation with fibrillogenicity. Biochemistry 1999 38 14101-14108. 

The determination of the character and location of phase transitions has been an active area of research from the early days of computer simulation, all the way back to the 1953 Metropolis et al. [59] MC paper. Within a two-phase coexistence region, small systems simulated under periodic boundary conditions show regions of apparent thermodynamic instability [60] simulations in the presence of an explicit interface eliminate this at some cost in system size and equilibration time. The determination of precise coexistence boundaries was usually done indirectly, through the... 

Cr-Al, Mn-Al, and Ti-Al alloys can be obtained from acidic melt solutions containing Cr(II), Mn(II), or Ti(II), respectively, only if the deposition potential is held very close to or slightly negative of the thermodynamic potential for the electrodeposition of aluminum, i.e., 0 V. From these observations it can be concluded that the formal potentials of the Cr(II)/Cr, Mn(II)/Mn, and Ti(II)/Ti couples may be equal to or less than E0 for the A1(III)/A1 couple. Unlike the Ag-Al, Co-Al, Cu-Al, Fe-Al, and Ni-Al alloys discussed above, bulk electrodeposits of Cr-Al, Mn-Al, and Ti-Al that contain substantial amounts of A1 can often be prepared because problems associated with the thermodynamic instability of these alloys in the plating solution are absent. The details of each of the alloy systems are discussed below. 

One additional problem at semiconductor/liquid electrolyte interfaces is the redox decomposition of the semiconductor itself.(24) Upon Illumination to create e- - h+ pairs, for example, all n-type semiconductor photoanodes are thermodynamically unstable with respect to anodic decomposition when immersed in the liquid electrolyte. This means that the oxidizing power of the photogenerated oxidizing equivalents (h+,s) is sufficiently great that the semiconductor can be destroyed. This thermodynamic instability 1s obviously a practical concern for photoanodes, since the kinetics for the anodic decomposition are often quite good. Indeed, no non-oxide n-type semiconductor has been demonstrated to be capable of evolving O2 from H2O (without surface modification), the anodic decomposition always dominates as in equations (6) and (7) for... 

Considering the small rotations involved with the effects we have observed and considering the thermodynamic instability of the poled configuration, one wonders about the factors which stabilize... 

Experience has shown that certain types of functional groups, which are frequently used, have a high thermodynamic instability and can be expected to release large amount of energy. 

Very often the carbon framework of the future allene is already present in the substrate and often it is propargylic in nature. For example, base-catalyzed isomeriza-tions of acetylenic hydrocarbons - with the triple bond in a non-terminal (40) or terminal position - were often used to prepare allenic hydrocarbons in the early days of allene chemistry [8]. The disadvantage of this approach consists in the thermodynamic instability of the allenes produced if not prohibited for structural reasons, the isomerizations do not stop at the allene but proceed to the more stable conjugated diene stage. In practice, complex mixtures are often formed [9] (see also Chapter 1). 

---