Hydrogen-methane-water system

Data for the hydrogen sulfide-water and the methane-n-hexane binary systems were considered. The first is a type III system in the binary phase diagram classification scheme of van Konynenburg and Scott. Experimental data from Selleck et al. (1952) were used. Carroll and Mather (1989a b) presented a new interpretation of these data and also new three phase data. In this work, only those VLE data from Selleck et al. (1952) that are consistent with the new data were used. Data for the methane-n-hexane system are available from Poston and McKetta (1966) and Lin et al. (1977). This is a type V system. 

Table 13.1). In the solid P(CH4) > P(CD4) but the curves cross below the melting point and the vapor pressure IE for the liquids is inverse (Pd > Ph). For water and methane Tc > Tc, but for water Pc > Pc and for methane Pc < Pc- As always, the primes designate the lighter isotopomer. At LV coexistence pliq(D20) < Pliq(H20) at all temperatures (remember the p s are molar, not mass, densities). For methane pliq(CD4) < pLiq(CH4) only at high temperature. At lower temperatures Pliq(CH4) < pliq(CD4). The critical density of H20 is greater than D20, but for methane pc(CH4) < pc(CD4). Isotope effects are large in the hydrogen and helium systems and pLIQ/ < pLiQ and P > P across the liquid range. Pc < Pc and pc < pc for both pairs. Vapor pressure and molar volume IE s are discussed in the context of the statistical theory of isotope effects in condensed phases in Chapters 5 and 12, respectively. The CS treatment in this chapter offers an alternative description.

Table 11.13 Deuterium fractionation in the water-hydrogen-methane system, after Bottinga (1969) (wv = water vapor, me = methane, hy = hydrogen).

The solubility of the components in the solvent must be sufficient. To improve the solubility, cosolvents can be used. Another possibility is the application of a two-phase system or an emulsion in the presence of phase-transfer catalysts. A two-phase system also has advantages in product isolation and continuous electrolysis procedures. A typical example is the synthesis of p-methoxy benzonitrile by anodic substitution of one methoxy group in 1,4-dimethoxybenzene by the cyanide ion (Eq. 22.21). The homogeneous cyanation system (acetonitrile, tetraethylammonium cyanide) [24] can be efficiently replaced by a phase-transfer system (dichloro-methane, water, sodium cyanide, tetrabutylammonium hydrogen sulfate) [71]. 

Soncini and Lazzeritti calculated the one- and two-bonds nuclear spin-spin coupling densities and the Fermi hole densities for hydrogen fluoride, water, ammonia, and methane molecules. The pair density function p2(xi, X2) determines the probability of two electrons being found simultaneously at points Xi = fiT]i and X2 = tit] , where i and fi are coordinates in three-dimensional space, and rii and TI2 are the spin variables of the two electrons. For a system described by a one determinant wavefunction of occupied spin-orbitals < >, (x), that is, a wavefunction in the HF approximation, the pair density function becomes... 

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