Thermodynamical stability

Frenkel D 1988 Thermodynamic stability of a smectic phase in a system of hard rods Nature 332 822-3... 

Mchale J M ef a/1996 Surface energies and thermodynamic stability in nanocrystalline aluminas Science 277 788... 

The composition of the products from the isomerization of an unsaturated compound under the influence of a catalytic amount of a base is governed by the relative thermodynamic stabilities of the starting compound and the product. Of particular synthetic interest are isomerizations in which there is an accumulation of an isomer in the isomerization sequence. Isolation of the desired intermediate in a reasonable state of purity is often a matter of careful selection of the base and the solvent. The following reactions are representative examples ... 

By protodetritiation of the thiazolium salt (152) and of 2 tritiothiamine (153) Kemp and O Brien (432) measured a kinetic isotope effect, of 2.7 for (152). They evaluated the rate of protonation of the corresponding yiides and found that the enzyme-mediated reaction of thiamine with pyruvate is at least 10 times faster than the maximum rate possible with 152. The scale of this rate ratio establishes the presence within the enzyme of a higher concentration of thiamine ylide than can be realized in water. Thus a major role of the enzyme might be to change the relative thermodynamic stabilities of thiamine and its ylide (432). 

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

Of the legion of partially saturated six-membered ring heterocycles, an idea of their stability, or lack of it, can normally be gained by consideration of the thermodynamic stability of the various components which can be identified in them. Thus, those rings which contain ester or amide functions can be expected to possess the chemical reactivity and the... 

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... 

The temperature at which this reaction is canied out is limited by considerations of the possibility of re-evaporation of As2 molecules and gallium atoms from the GaAs him. The semiconduchng compounds are less susceptible to this problem than the separate elements because of the thermodynamic stabilities of diese compounds, as discussed above. 

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. 

As pointed out in Section 2.4, shock waves are such rapid processes that there is no time for heat to flow into the system from the surroundings they are considered to be adiabatic. By the second law of thermodynamics, the quantity (S — Sg) must be positive for any thermodynamic process in an isolated system. According to (2.54), this quantity can only be positive if the P-V isentrope is concave upward. Thus, the thermodynamic stability condition for a shock wave is... 

The thermodynamic stability of a protein in its native state is small and depends on the differences in entropy and enthalpy between the native state and the unfolded state. From the biological point of view it is important that this free energy difference is small because cells must be able to degrade proteins as well as synthesize them, and the functions of many proteins require structural flexibility. 

It has been found that there is often a correlation between the rate of deprotonation (kinetic acidity) and the thermodynamic stability of the carbanion (thermodynamic acidity). Because of this relationship, kinetic measurements can be used to construct orders of hydrocarbon acidities. These kinetic measurements have the advantage of not requiring the presence of a measurable concentration of the carbanion at any time instead, the relative ease of carbanion formation is judged from the rate at which exchange occurs. This method is therefore applicable to very weak acids, for which no suitable base will generate a measurable carbanion concentration. 

The relative stability of the intermediates determines the position of substitution under kinetically controlled conditions. For naphthalene, the preferred site for electrophilic attack is the 1-position. Two factors can result in substitution at the 2-position. If the electrophile is very bulky, the hydrogen on the adjacent ring may cause a steric preference for attack at C-2. Under conditions of reversible substitution, where relative thermodynamic stability is the controlling factor, 2-substitution is frequently preferred. An example of this behavior is in sulfonation, where low-temperature reaction gives the 1-isomer but at elevated temperatures the 2-isomer is formed. ... 

The toroidal and helical forms that we consider here are created as such examples these forms have quite interesting geometrical properties that may lead to interesting electrical and magnetic properties, as well as nonlinear optical properties. Although the method of the simulations through which we evaluate the reality of the structure we have imagined is omitted, the construction of toroidal forms and their properties, especially their thermodynamic stability, are discussed in detail. Recent experimental results on toroidal and helically coiled forms are compared with theoretical predictions. 

We showed the possible existence of various forms of helically coiled and toroidal structures based on energetic and thermodynamic stability considerations. Though the formation process of these structures is not the subject of this work, the variety of patterns in the outer and inner surface of the structures indicates that there exist many different forms of stable cage carbon structures[10-19]. The molecules in a onedimensional chain, or a two-dimensional plane, or a three-dimensional supermolecule are possible extended structures of tori with rich applications. 

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. 

The yields of thermal rearrangements of some perfluorinated olefins are very low The fact that perfluorocyclobutene yields perfluoro-l,3-butadiene at 650 °C only in a 12% yield [7] is due to the higher thermodynamic stability of perfluoro cyclobutene compared with the-open chain product [72 ]... 

Rearrangement studies give an interesting insight into the specific effect of fluonne on the thermodynamic stability and rearrangement kinetics of fluonnated cyclopropanes Fluorine decreases the thermodynamic stability of the cyclopropyl nng, in contrast with the generally observed effect of fluonne increasing the stability of molecules to which it is introduced [124]... 

The greater thermodynamic stability of iodates enables iodine to displace CI2 and Bt2 from their halates ... 

In keeping with the thermodynamic stability of the ene-hydrazine, the mono-phenylhydrazone of cyclohexane-1,3-dione 38 provided only one of two possible isomers 39, or at least, one dominant product 39 on indolization. ... 

Two independent molecular orbital calculations (HMO method) of delocalization energies for isoindole and isoindolenine tautomers agree that the isoindole form should possess the more resonance stabilization. The actual difference calculated for isoindole-isoindolenine is about 8 kcal/mole, but increases in favor of the isoindole with phenyl substitution at position 1 (Table VI).Since isoindole and isoindolenine tautomers have roughly comparable thermodynamic stabilities, the tautomeric proce.ss is readily obser-... 

The increase in thermodynamic stability of 85 is achieved by easy ring opening (01H127). This knowledge allows one to control the regioselectivity of the oxidative amination of the 6-aryl-l,2,4-tiiazine 4-oxides 53, obtaining either (i) the 5-amino-1,2,4-triazine 4-oxides 56 in the reaction of 53 with amines at low temperature in the presence of the oxidant or (ii) the 3-amino-1,2,4-triazine 4-oxides 88, provided the reaction is carried out in two steps (addition and oxidation) at room temperature or higher. 

Molecular mechanics calculations with the molecular mechanics force field program were performed to compare thermodynamic stability among araguspongine B (17) (containing two cw-fused perhydropyrido[2,l-Z>] [l,3]oxazine bicycles), araguspongine D (18) (containing two tran -fused perhydropyrido[2,l-Z)][l,3]oxazine bicycles), and araguspongine E (19)... 

The activation energies were computed to 3.0 (toward 183), 0.3 (toward 182), and 21.8 kcal/mol (toward 184) at the B3-LYP/6-31G level, and thus the mechanism leading to 182 is the preferred one. The transition states of all three reactions belong to concerted but asynchronous reaction paths. The transacetalization of 177 with acylium cations results in the formation of the thermodynamically stabilized 187 (Scheme 121) [97JCS(P2)2105]. 186 is less stable than 187, and 185 is destabilized by 32.5 kcal/mol. Moreover, transacetalization of 177 with sulfinyl cations is not a general reaction. Further computational studies on dioxanes cover electrophilic additions to methylenedioxanes [98JCS(P2)1129] and the influence... 

The thermodynamic stabilities of three possible annular tautomers of the parent 1,2,4,5-thiatriazine 134 were compared using ab initio HF/6-31G calculations (OOJOC931). The 4H isomer 134a appears to be the most stable (it is more stable than 134b by 11.6 kcal/mol and more stable than 134c by 15.5 kcal/mol), presumably because it allows low-energy distortion from planarity and formation of the boat conformation. 

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