Favored equilibrium

A protomeric equilibrium favors the acetamido rather than the acetimido form (105, 121). The parent molecular ion has been reported to be absent in the mass spectrum of 2-acylaminothiazoles (130). 

The reaction is endothermic and the equilibrium favors ethylene at low temperatures but shifts to favor acetylene above 1150°C Indeed at very high temperatures most hydro carbons even methane are converted to acetylene Acetylene has value not only by itself but IS also the starting material from which higher alkynes are prepared... 

The Kolbe-Schmitt reaction is an equilibrium process governed by thermodynamic control The position of equilibrium favors formation of the weaker base (salicylate ion) at the expense of the stronger one (phenoxide ion) Thermodynamic control is also responsible for the pronounced bias toward ortho over para substitution Salicylate anion IS a weaker base than p hydroxybenzoate and predominates at equilibrium... 

An unfavorable methyl-methyl interaction destabilizes the s-trans conformation of 4-methyl-3-penten-2-one relative to the s-cis conformation, and the equilibrium favors the s-cis form. 

Below — 140°C, the EPR spectrum observed was that of the cyclopropylmethyl radical. If the photolysis was done above — 140°C, however, the spectmm of a second species was seen, and above — 100°C, this was the only spectmm observed. This second spectmm could be shown to be that of the 3-butenyl radical. This study also established that the 3-butenyl radical did not revert to the cyclopropylmethyl radical on being cooled back to — 140°C. The conclusion is that the ring opening of the cyclopropyl radical is a very facile process and that the lifetime of the cyclopropyl radical above — 100°C is very short. Even though the equilibrium favors the 3-butenyl radical, the reversible ring closure can be detected by isotopic labeling experiments, which reveal the occurrence of deuterium migration ... 

The sluggishness of the reaction of TIPSOTf with tertiary alcohols can be exploited to advantage, as was the case in Magnus synthesis of strychnine. The equilibrium favors the tertiary hemiketal, but silylation favors the primary alcohol. 

The tautomeric equilibrium 151 152 has been discussed by Cromwell and David.Ultraviolet spectral data indicate that 151 predominates in neutral aqueous solution, and infrared data are in essential agreement. It was further concluded that in acid solution the equilibrium favors 152, but no ionization constants were reported,... 

Cyanohydrin formation is somewhat unusual because it is one of the few examples of the addition of a protic acid (H—Y) to a carbonyl group. As noted in the previous section, protic adds such as H20, HBr, HC1, and H2S04 don t normally yield carbonyl addition products because the equilibrium constants ate unfavorable. With HCN, however, the equilibrium favors the cyanohydrin adduct. 

Both reactions are reversible, and the position of the equilibrium depends on the specific case. In general, the triene cyclohexadiene equilibrium favors the cyclic product, whereas the diene cyclobutene equilibrium favors the unstrained open-chain product. 

The Haber process, represented by this equation, is now the main source of fixed nitrogen. Its feasibility depends on choosing conditions under which nitrogen and hydrogen react rapidly to give a high yield of ammonia. At 25°C and atmospheric pressure, the position of the equilibrium favors the formation of NH3 (K= 6 x 105). Unfortunately. however, the rate of reaction is virtually zero. Equilibrium is reached more rapidly by raising the temperature. However, because... 

This distinction between the conditions in a chemical system at equilibrium and the rate at which these conditions are attained is very important in chemistry. By arguments that we shall consider a chemist can decide with confidence whether equilibrium favors reactants or products or neither. He cannot predict, however, how rapidly the system will approach the equilibrium conditions. That is a matter of reaction rates, and the chemist must perform separate experiments to learn whether a given rate is rapid or not. 

Despite this detailed familiarity with equilibrium, there is one facet we have not considered at all. What determines the equilibrium constant Why does one reaction favor reactants and another reaction favor products What factors cause sodium chloride to have a large solubility in water and silver chloride to have a low solubility Why does equilibrium favor the reaction of oxygen with iron to form FejAi (rust) but not the reaction of oxygen with gold As scientists, we cannot resist wondering what factors determine the conditions at equilibrium. 

The equilibrium state is a compromise between these two factors, minimum energy and maximum randomness. At very low temperatures, energy tends to be the more important factor. Then equilibrium favors the molecular substances with the... 

The same sort of competition for electrons is involved in reaction (11), in which Zn(s) releases electrons and Cu+2 accepts them. This time the competition for electrons is such that equilibrium favors Zn+2 and Cu(s). By way of contrast, compare the reaction of metallic cobalt placed in a nickel sulfate solution. A reaction occurs,... 

The value of this list is obvious. Any half-reaction can be combined with the reverse of another half-reaction (in the proportion for which electrons gained is equal to electrons lost) to give a possible chemical reaction. Our list permits us to predict whether equilibrium favors reactants or products. We would like to expand our list and to make it more quantitative. Electrochemical cells help us do this. 

The negative voltage shows that the state of equilibrium favors the reactants more than the products for the reaction as written. For standard conditions, the reaction will not tend to occur spontaneously. However, if we place Ag(s) in 1 M H+, the Ag+ concentration is not 1 M— it is zero. By Le Chatelier s Principle, this increases the tendency to form products, in opposition to our prediction of no reaction. Some silver will dissolve, though only a minute amount because silver metal releases electrons so reluctantly compared with H2. It is such a small amount, in fact, that no silver chloride precipitate forms, even though silver chloride has a very low solubility. 

Consider two reactions for which ° shows that products are favored, one an exothermic reaction, and the other an endothermic reaction. For the exothermic reaction, when the reactants are mixed they are driven toward equilibrium in accord with the tendency toward minimum energy. Now contrast the endothermic reaction for which ° shows that equilibrium favors products. When these reactants are mixed, they approach equilibrium against the tendency toward minimum energy (since heat is absorbed). This reaction is driven by the tendency toward maximum randomness. 

Large values of K (larger than about 103) the equilibrium favors the products. 

In hemoglobin M, histidine F8 (His F8) has been replaced by tyrosine. The iron of HbM forms a tight ionic complex with the phenolate anion of tyrosine that stabilizes the Fc3 form. In a-chain hemoglobin M variants, the R-T equilibrium favors the T state. Oxygen affinity is reduced, and the Bohr effect is absent. P Ghain hemoglobin M variants exhibit R-T switching, and the Bohr effect is therefore present. 

Rearrangement can also occur after the initial alkylation. The reaction of 2-chloro-2-methylbutane with benzene is an example of this behavior.35 With relatively mild Friedel-Crafts catalysts such as BF3 or FeCl3, the main product is 1. With A1C13, equilibration of 1 and 2 occurs and the equilibrium favors 2. The rearrangement is the result of product equilibration via reversibly formed carbocations. 

The pyrimido[2,T ][l>3]oxazines 301 are sensitive to water and suffer reversible ring opening to the lactams 302. The equilibrium favors the ring-opened product (Equation 31) <20050BC1964>. 

Mercapto-l,2,4-thiadiazoles exist as an equilibrium of tautomers with the equilibrium favoring the thione tautomer. They are acidic with a pA a of around 5. A variety of methylating agents (e.g., diazomethane, dimethyl sulfate and methyl iodide) give S-methylated products and no N-methylation has been observed. They are readily oxidized to sulfoxides and sulfones with either z-chloroperbenzoic acid or hydrogen peroxide in acetic acid <1996CHEC-II(4)307>. There have been no new publications on S-linked substituents since the publication of CHEC-II(1996). 

The first reaction (Boudouard equilibrium) favors carbon formation at lower temperatures compared to POX. The hydrogen concentrations attained depend on the fuel used in POX but it never reaches the theoretical level [27],... 

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