Hydroquinone clathrate

Examples of the hydroquinone inclusion compounds (91,93) are those formed with HCl, H2S, SO2, CH OH, HCOOH, CH CN (but not with C2H 0H, CH COOH or any other nitrile), benzene, thiophene, CH, noble gases, and other substances that can fit and remain inside the 0.4 nm cavities of the host crystals. That is, clathration of hydroquinone is essentially physical in nature, not chemical. A less than stoichiometric ratio of the guest may result, indicating that not all void spaces are occupied during formation of the framework. Hydroquinone clathrates are very stable at atmospheric pressure and room temperature. Thermodynamic studies suggest them to be entropic in nature (88). 

HC1 2H20 and HC1 3H20 it readily forms a hydroquinone clathrate. Ammonia, on the other hand, does not form clathrates with either water or hydroquinone. Molecules with a very low polarizability (He, Ne, H2) are not known to form clathrate solutions by themselves, but they do help to stabilize the clathrate of a more polarizable solute simultaneously present.47 It is almost needless to say that in the following we shall only consider those hydrates which are in fact clathrates and which are frequently referred to as gas hydrates/ although the molecules of certain volatile liquids may also be included. 

In the next section we shall give a brief account of the crystal structure of the hydroquinone clathrates and of the gas hydrates, as far as is needed for a proper understanding of the subsequent parts. The reader who is interested in the phenomenology of other clathrate compounds should consult one of the many review articles7,8 39 on inclusion compounds. 

Fig. 1. The crystal structure of a hydroquinone clathrate according to Palin and Powell. 8 The balls inside the transparent spheres represent argon atoms encaged in the cavities formed by the two interpenetrating lattices, (photograph kindly supplied by Dr. Powell).

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

One important difference between the present and the previous case should be noted. For the hydroquinone clathrates, where the wall of a cavity consists of 12 OH groups, 6 adjacent carbon atoms, and 6 CH groups in ortho position to the OH groups, it seemed best to consider the product z qjk) as one unknown. For hydrates one may not do this the walls of both types of cavities consist exclusively of tetrahedrally-coordinated water molecules. Hence, one should use the same value of (,eg/k) —characteristic for a water molecule in a hydrate lattice—for both types of cavities and multi-... 

For the hydroquinone clathrates it was possible to make a direct comparison between the heat observed for the reaction... 

Nuclear magnetic resonance spectroscopy of the solutes in clathrates and low temperature specific heat measurements are thought to be particularly promising methods for providing more detailed information on the rotational freedom of the solute molecules and their interaction with the host lattice. The absence of electron paramagnetic resonance of the oxygen molecule in a hydroquinone clathrate has already been explained on the basis of weak orientational effects by Meyer, O Brien, and van Vleck.18... 

The points R have to be on a straight line terminating in the composition of the methanol hydroquinone clathrate (A) in equilibrium with a-hydroquinone at 25°C. The point B roughly corresponds to the composition of the clathrate obtained by Palin and Powell24 when crystallizing hydroquinone from methanol points between A and B form a continuous range of solid solutions in equilibrium with liquid phases whose compositions lie on the curve CE. It is found that the equilibrium clathrate has a composition corresponding to y — 0.474 at 25°C. 

The composition of the hydrates varies with temperature along the three-phase lines H ice G and HL2G in a way similar to that described for the system hydroquinone-argon. But as already noted in Section II.D this variation is smaller than for the hydroquinone clathrates. Accordingly, a cross section through the P-T-x diagram at constant temperature below 0°C would reveal a two-phase area G+H in which the composition of the latter is less sensitive to pressure than found in the corresponding case for the hydroquinone clathrates (cf. Fig. 4). 

Kroll process, 13 84-85 15 337 17 140 in titanium manufacture, 24 851-853 Kroll zirconium reduction process, 26 631 KRW gasifier, 6 797-798, 828 Krypton (Kr), 17 344 commercial, 17 368t complex salts of, 17 333-334 doubly ionized, 14 685 hydroquinone clathrate of, 14 183 in light sources, 17 371-372 from nuclear power plants, 17 362 physical properties of, 17 350 Krypton-85, 17 375, 376 Krypton compounds, 17 333-334 Krypton derivatives, 17 334 Krypton difluoride, 17 333, 336 uses for, 17 336... 

Daschbach, J. L., Chang, T. M., Corrales, L. R., Dang, L. X., McGrail, P., Molecular mechanisms of hydrogen-loaded beta-hydroquinone clathrate. J. Phys. Chem. B 2006, 110, 17291-17295. 

The lattice of the host in the form it takes in the clathrate is usually thermodynamically unstable by itself—that is, with the holes empty. It is stabilized by inclusion of the guest molecules, and it is of obvious interest in connection with the nonstoichiometry of clathrates to consider the extent to which the cavities in the host lattice must be filled before the system achieves thermodynamic stability. The cavities in the host lattice may all be identical in size and environment, as in the hydroquinone clathrates, or they may be of more than one kind. The gas hydrates, for example, have two possible structures, in each of which there are two sorts of cavity, van der Waals and Platteeuw (15) have developed a general statistical theory of clathrates containing more than one type of cavity. 

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