Thermodynamically unfavorable

These reactions are thermodynamically unfavorable at temperatures below ca 1500°C. However, at temperatures in the range from 1000 to 1200°C a small but finite equiUbrium pressure of barium vapor is formed at the reaction site. By means of a vacuum pump, the barium vapor can be transported to a cooled region of the reactor where condensation takes place. This destroys the equiUbrium at the reaction site and allows more barium vapor to be formed. The process is completely analogous to that used in the thermal reduction of CaO with aluminum to produce metallic calcium (see Calcium AND CALCIUM alloys). 

Aluminothermal Method. Calcium metal is produced by high temperature vacuum reduction of calcium oxide in the aluminothermal process. This process, in which aluminum [7429-90-5] metal serves as the reducing agent, was commercialized in the 1940s. The reactions, which are thermodynamically unfavorable at temperatures below 2000°C, have been summarized as ... 

The principle of microscopic reversibility requires that the reverse process, ring closure of a butadiene to a cyclobutene, must also be a coiuotatory process. Usually, this is thermodynamically unfavorable, but a case in which the ring closure is energetically favorable is conversion of tra s,cis-2,4-cyclooctadiene (1) to bicyclo[4.2.0]oct-7-ene (2). The ring closure is favorable in this case because of the strain associated with the trans double bond. The ring closure occurs by a coiuotatory process. 

A negative AE indicates an exothermic (thermodynamically favorable) reaction, while a positive AE an endothermic (thermodynamically unfavorable) reaction. 

Conjugate addition of methyl magnesium iodide in the presence of cuprous chloride to the enone (91) leads to the la-methyl product mesterolone (92) Although this is the thermodynamically unfavored axially disposed product, no possibility for isomerization exists in this case, since the ketone is once removed from this center. In an interesting synthesis of an oxa steroid, the enone (91) is first oxidized with lead tetraacetate the carbon at the 2 position is lost, affording the acid aldehyde. Reduction of this intermediate, also shown in the lactol form, with sodium borohydride affords the steroid lactone oxandrolone... 

Carbon Laydown. The potential for carbon laydown is readily estimated from the thermodynamics of Reactions 4 and 5. The areas where carbon laydown, according to these reactions, is thermodynamically possible were developed by Gruber (36). It is readily seen that carbon laydown via Reaction 4 is thermodynamically favorable at the reactor inlet for practically any commercially conceivable feed gas composition. As noted by Gruber (36), carbon laydown is thermodynamically unfavorable at the reactor outlet for practically all commercially conceivable methanator conditions. The methanation reactor will therefore, in practice, have two zones—the first is a finite zone between the inlet and some way down the catalyst bed where carbon laydown is thermodynamically possible, and the second zone is the balance of the reactor. 

Aldehydes up to a chain length of four nonhydrogen atoms are tolerated as acceptors. 2-Hydroxyaldehydes are relatively good acceptors, and the D-isomers are preferred over the t-isomers [180]. Reactions that lead to thermodynamically unfavorable structures may proceed with low stereoselectivity at the reaction center [181]. Recently, a single-point mutant aldolase was found 2.5 times more effective than the wild type in accepting unphosphorylated glyceraldehyde [182,183]. 

The addition of metal hydrides to C—C or C—O multiple bonds is a fundamental step in the transition metal catalyzed reactions of many substrates. Both kinetic and thermodynamic effects are important in the success of these reactions, and the rhodium porphyrin chemistry has been important in understanding the thermochemical aspects of these processes, particularly in terms of bond energies. For example, for first-row elements. M—C bond energies arc typically in the range of 2, i-. i() kcal mol. M—H bond energies are usually 25-30 kcal mol. stronger, and as a result, addition of M—CH bonds to CO or simple hydrocarbons is thermodynamically unfavorable. 

ATP Allows the Coupling of Thermodynamically Unfavorable Reactions to Favorable Ones... 

The overall change in free energy for the catalytic reaction equals that of the uncatalyzed reaction. Hence, the catalyst does not affect the equilibrium constant for the overall reaction of A -i- B to P. Thus, if a reaction is thermodynamically unfavorable, a catalyst cannot change this situation. A catalyst changes the kinetics but not the thermodynamics. 

In marked contrast to the reaction with (ArS)2, the l l-adduct 85 was not formed at all. The stoichiometric study also supported this fact, indicating that the formation of 85 from (ArSe)2 with 73 is a thermodynamically unfavorable process. 

Possibility of significant equilibrium shift in the desired direction. Thermodynamically unfavorable reactions become possible. 

Another possible source of modification of the HBI optical properties arises from cis-trans (or, more properly, Z-E) isomerization around its exocyclic ethylene bridge (dihedral angle x as depicted in Fig. 3a) [74, 75]. The absorption spectrum of trans HBI in different solvents is red-shifted by 5-10 nm compared to that of the cis conformation [76]. While the trans conformation is thermodynamically unfavorable and contributes only a minor population at room temperature, cis-trans isomerization seems to take place regardless of the chromophore ionization state, and involves a relatively low energy barrier of about 50 kJ/mol [75], a value that appears significantly lower than initially predicted from quantum mechanics [77, 78]. 

Most remarkably, the homoallylic halides 214 not only yield the thermodynamically unfavored ris-cyclopropanes 215 preferentially (see Sect. 2.2.3), but also give rise to enantioselective formation of the (1/ ) configuration, in contrast to the cyclopropanation of 1,3-butadienes with the same catalysts (see Table 15). Only in the case of olefin 214 (X = CF3, Y = Cl), may the (1 S)-trans isomer be obtained enantioselecti-vely, depending on the catalyst (Table 16, entries 8-11). In these few cases, optical induction occurs at C(3) of the cyclopropane rather than at C(l). 

Electrochemical sensors, however, currently share one key advantage an excitation signal may be imposed that can trigger a sensing reaction, and the energy required for an otherwise thermodynamically unfavorable extraction and/or binding process can be... 

From the chemical point of view, the solvent in which the CL experiment is carried out can have a dramatic influence on the efficiency of the CL reaction as solvation can alter the shapes, the depths, and the densities of the vibrational states of the potential surfaces representing the ground states of products and reactants and the lowest excited singlet state of the potential fluorophore. The alteration of the intersections of these potential energy surfaces can affect the enthalpies of reaction and the enthalpies of activation for dark and lumigenic reactions. In some cases, these changes will favor CL (if AH decreases relative to AHa) and in some cases, they will make it thermodynamically unfavorable for CL to occur. 

Actually, in these derivatives the silicon atom bonded to the oxygen atom of the nitro group contains no protons. Hence, decomposition according to Eq. 1 is impossible. The fragmentation according to Eq. 2 is also unlikely because the Si=C double bond is thermodynamically unfavorable. 

Lehnert and Tuczek further studied end-on terminal coordination by density functional theory (DFT) calculations on the compounds [Mo(N2)2(dppe)2], [MoF(NNH)(dppe)2], and [MoF(NNH2)(dppe)2]+, where dppe= 1,2-bis(diphenyl-phosphino)ethane.50 They proposed a reaction scheme, shown in reaction 6.13, for asymmetric dinitrogen reduction and protonation. The end-on model favored by Lehnert in reference 50, as shown in reaction 6.13, appears to be a less thermodynamically unfavorable pathway, at least to reach the M-NNH3 intermediate. Step 1 produces a metal-attached diazenido ion (NNH-), step 2 produces a hydrazido ion (NNH2 ), and step 3 produces a hydrazidium ion (NNHj). 

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