Equilibration condensation

In the condensation of 2-butanone with citral, if the reaction temperature is kept at 0—10°C, higher yields of the isomethyl pseudoionones, which are the more thermodynamically stable isomers, are obtained. The aldol iatermediates have more time to equilibrate to the more stable isomers at the lower temperature. The type of base used and a cosolvent such as methanol are also very important ia getting a high yield of the isomethyl pseudoionones (168). 

The second stage of the process is to condition the beads, necessary because on cooling after prefoaming pneumatogen and steam within the cells condense and cause a partial vacuum within the cell. By allowing the beads to stand in air for at least 24 hours air can diffuse into the cells in order that at room temperature the pressure within the cell equilibrates with that outside. 

For the other broad category of reaction conditions, the reaction proceeds under conditions of thermodynamic control. This can result from several factors. Aldol condensations can be effected for many compounds using less than a stoichiometric amount of base. Under these conditions, the aldol reaction is reversible, and the product ratio will be determined by the relative stability of the various possible products. Conditions of thermodynamic control also permit equilibration among all the enolates of the nucleophile. The conditions that permit equilibration include higher reaction temperatures, protic solvents, and the use of less tightly coordinating cations. 

Clearly, there are situations where we have to give up this assumption. A typical case is molecular beam epitaxy (MBE) (see [3,12-14] and [15-19]), where particles are shot onto the surface of a crystal rather than condensing slowly from a thermally equilibrated vapor-phase. In this case we will have to be very specific about all the experimental boundary conditions and... 

In a reaction similar to 12-50, azoxy compounds can be prepared by the condensation of a nitroso compound with a hydroxylamine. The position of the oxygen in the final product is determined by the nature of the R groups, not by which R groups came from which starting compound. Both R and R can be alkyl or aryl, but when two different aryl groups are involved, mixtures of azoxy compounds (ArNONAr, ArNONAr, and Ar NONAr ) are obtained and the unsymmetrical product (ArNONAr ) is likely to be formed in the smallest amount. This behavior is probably caused by an equilibration between the starting compounds prior to the actual reaction (ArNO -I- Ar NHOH Ar NO - - ArNHOH). The mechanism has been investigated in the presence of base. Under these conditions both reactants are converted to radical anions, which couple ... 

Maier and co-workers condensed formaldehyde and elemental silicon at 12 K in an argon matrix and photolyzed the mixture to form silaketene H2SiCO, which is similar in structure to the silylene-CO adduct mentioned above. The reactants first form siloxiranylidene 49 (which equilibrates with an unknown species postulated as the planar/linear silaketene 50 when exposed to 313-nm-wavelength light) and then forms complex 51 when photolyzed at 366 nm (Scheme 15). This species could also be formed by photolyzing diazidosilane 52 in the presence of CO, and complex 51 equilibrates with SiCO (53) and H2. The CO infrared shift for this bent structure was calculated at 2129 cm , which is shifted —80cm from the calculated value of free CO, at 2210 cm. The experimentally observed value was reported at 2038-2047 cm at 12 K. 

Droplets of various hquids were prepared in several ways. For example, a macroscopic drop was first deposited on the substrate and then absorbed from an edge using filter paper. In other cases a macroscopic drop was blown away with a jet of N2 or air. These processes leave a surface that appears dry to the naked eye but still contains many tiny droplets that can be observed with SPFM. If the droplets are of aqueous solutions, the water vapor pressure in the chamber, with which they readily equilibrate, determines their size. For hquids with low vapor pressure, films and droplets can be formed by condensation from a warmed reservoir. 

This type of cake is often stored for a while after baking because it is to be covered with royal icing. The cake not only needs to cool but the surface needs to equilibrate with the bulk. There is a paradox that if the cake is just wrapped in greaseproof paper and kept in a tin that is not air tight there will be no problem. However, if the cake is wrapped in aluminium foil and kept in an air tight tin there is a possibility of mould formation because with the better moisture barrier any condensation or sweating can not evaporate. 

In the isopiestic method two condensed phases are equilibrated via the gas phase [104,105]. The composition and pressure of the gas phase are determined by use of a reference compound for which the partial pressure of a volatile component... 

Lehn, which was obtained from a dynamic library of hydrogen-bonding building blocks [101]. This system involved the equilibration between different products resulting from the condensation of 5,5-dimethyl-1,3-cyclohexanedione (74) and 2-hydrazinopyridine (75) (see Scheme 38). 

The understanding of isotope effects on chemical equilibria, condensed phase equilibria, isotope separation, rates of reaction, and geochemical and meteorological phenomena, share a common foundation, which is the statistical thermodynamic treatment of isotopic differences on the properties of equilibrating species. For that reason the theory of isotope effects on equilibrium constants will be explored in considerable detail in this chapter. The results will carry over to later chapters which treat kinetic isotope effects, condensed phase phenomena, isotope separation, geochemical and biological fractionation, etc. 

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