Clathrates 31, Table

Table III shows the vapor pressures of some hydroquinone clathrates at 25°C calculated according to Eq. 38, and Table IV...

Let us first consider the three-phase equilibrium ( -clathrate-gas, for which the values of P and x = 3/( +3) were determined at 25°C. When the temperature is raised the argon content in the clathrate diminishes according to Eq. 27, while the pressure can be calculated from Eq. 38 by taking yA values following from Eq. 27 and the same force constants as used in the calculation of Table III. It is seen that the experimental results at 60°C and 120°C fall on the line so calculated. At a certain temperature and pressure, solid Qa will also be able to coexist with a solution of argon in liquid hydroquinone at this point (R) the three-phase line -clathrate-gas is intersected by the three-phase line -liquid-gas. At the quadruple point R solid a-hydroquinone (Qa), a hydroquinone-rich liquid (L), the clathrate (C), and a gas phase are in equilibrium the composition of the latter lies outside the part of the F-x projection drawn in Fig. 3. The slope of the three-phase line AR must be very steep, because of the low solubility of argon in liquid hydroquinone. 

Table 1 Types of Cd(CN)2 and related clathrates, space groups and examples.

The detailed structures of several clathrates have been characterized, and a certain degree of selectivity on complexation with different isomers has been detected 21). Most of these complexes are of the channel type, but some of them have structures which simultaneously qualify for channel and cage type descriptors representative examples are illustrated in Figs. 19-21. The crystal data of the complexes are summarized in Table 1. 

Table 1. Clathrate inclusion compounds of I stoichiometries and thermal stability characterization...

Table 3. Clathrate inclusion compounds of scissor-like hosts other than 1...

Table 5. Clathrate inclusion compounds of roof-shaped hosts...

The family of true clathrates based on hydrocarbons only is further enriched by the inclusion compounds of 48 with benzene (1 1) and p-xylene (2 1) 90> (Table 19). Figure 28 illustrates the structure of 48 benzene (1 1). The structure of the p-xylene clathrate shows intercalated guest molecules at centers of symmetry in the crystal lattice. Both clathrates are rather unstable at ambient temperatures and decompose easily, e.g. on exposure to X-rays (even in the presences of mother liquor). The 48 p-xylene clathrate is unstable to such a degree that decomposition occurs at low temperature. 

Bulk polymerization of //r/ .v-2-melhyI-1,3-pcntadiene lead only to 1,4-trans addition polymer, however it allows randomization of the trans structure, leading to an atactic polymer. The polymerization of the clathrate of rraw.v-2-mclhyl-1,3-pcntadiene yielded an isotactic 1,4-trans addition polymer. The polymer formed from the bulk had a molecular weight of 20,000 (240 monomer units), and that formed from the clathrate had a molecular weight of 1000 (12 monomer units). Similar results were obtained for other dienes, and the results are summarized in Table 4. It can be concluded that polymerization of dienes in the clathrate lead exclusively to a 1 A-lrans addition polymer, except in the case of 1,3-cyclohexadiene. For this monomer, although the polymer is formed entirely by 1,4-addition, the polymer formed is essentially atactic. In bulk polymerization, the polymerization proceeds in most cases through 1,4-addition (both trans and cis), but in the case of butadiene and 1,3-cyclohexadiene 1,2-additions were also observed. Actually, in the case of the bulk /-induced polymerization of 1,3-cyclohexadiene the 1,2-addition process was favoured over the 1,4-addition process by a ratio of 4 3. 

Cadmium cyanide, CdCCN), is analogous to Si02 with respect to the AB2 composition, the tetrahedral confiugration of A, the bridging behavior of B between a pair of A atoms, and the ability to build a three-dimensional framework in which cavities of molecular scale are formed. Cadmium caynide itself crystallizes in a cubic system of the anticuprite type, in which two identical fr-cristobalite-like frameworks interpenetrate each other without any cross-connection the cavity formed in one framework is filled by the other. When we replace one of the frameworks by appropriate guest molecules such as those of CCl, CCl CH, etc., we may obtain a novel clathrate structure with an adamantane-like cavity, as shown in Fig. 1 [1], Our results including those recently obtained are summarized in Table 1. 

Illustrative examples of substances which can behave as porous hosts in one of the above ways are also given. For instance, water readily forms open ice lattices which incorporate guests in clathrate hydrates of types I and II (see later text). Ordinary ice also possesses considerable porosity so that, as shown in Table I, He and Ne can readily diffuse through it. Ice below 0°C is zeolite-like in that it has a permanent, somewhat porous structure which (unlike the open-ice frameworks of the clathrate hydrates) does not require guest molecules for stabilization. 

Tabushi et al. (1981) suggested that the 15-hedron (51263) is absent from Figure 2.5 and in all clathrates except bromine due to an unfavorable strain relative to the other cavities in si and sll. In their review of simple and combined cavities, Dyadin et al. (1991) suggested that in addition to the cavities found in si, sll, and sH, there are 4258 and 51263 cavities. In Jeffrey s (1984) list of a series of seven hydrate crystal structures (Table 2.3), additional cavities to those found in si, sll, and sH are 51263, 4454,43596273, 4668. 

Tables 2.5a,b provide a comprehensive list of guest molecules forming simple si and sll clathrate hydrates. The type of structure formed and the measured lattice parameter, a, obtained from x-ray or neutron diffraction are listed. Unless indicated by a reference number, the cell dimension is the 0°C value given by von Stackelberg and Jahns (1954). Where no x-ray data exists, assignment of structure I or II is based on composition studies and/or the size of the guest molecule. Tables 2.5a,b also indicate the year the hydrate former was first reported, the temperature (°C) for the stable hydrate structure at 1 atm, and the temperatures (°C) and pressures (atm) of the invariant points (Qi and Q2). Both cyclopropane and trimethylene oxide can form si or sll hydrates. Much of the contents of these tables have been extracted from the excellent review article by Davidson (1973), with updated information from more recent sources (as indicated in the tables).

Kini (2002). The Raman data are based on the works by Sum (1996), Tulk et al. (1998), Subramanian (2000), and Hester (2007). To accompany these tables, select NMR and Raman spectra are given in Figures 6.13 through 6.19. These tables and sample spectra should serve as a useful reference to those embarking on spectroscopic measurements and analysis of clathrate hydrates. 

Table 4 Selected bond lengths (A), bond angles (°), and dihedral angles (°) of thiepine 19 in clathrates 19-dioxane and 19-1/2 benzene...

Liquid clathrates offer a great advantage over solid-state separations (e.g. by formation of Hoffman-type inclusion compounds, Section 9.4) because of the extremely fast mixing kinetics, the avoidance of the need to wait for crystallisation to occur and the easy separation of the two liquid phases. It should also prove possible to run liquid clathrate separations in a continuous extraction manner. The avalues of a number of liquid clathrate-based separations have been reported and are summarised in Table 13.1. 

Table 13.1 Liquid clathrate-based separations of 1 1 feed mixtures.

Noble gas clathrates will not now form on the Earth, as can be seen from the air pressure decomposition temperatures in Table 2.7. They might, however, form in cooler regions of the primitive solar nebula (see Limine Stevenson, 1985). Sill and Wilkening (1978) note that for pressures in a plausible model nebula, pure ice clathrates of Ar, Kr, and Xe could form at 40, 45, and 62 K, respectively. 

Table 2.7. Decomposition vapor pressure data for ice-noble gas clathrates...

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