Hydrogen Bonding—Thermal Relations

The molar heat capacity (molar thermal capacity), which is the energy required to increase the temperature of 1 mol by 1°C, is 75.4 J mol-1 °C-1 for water. The energy to heat water from 0°C to 25°C therefore is 

Van der Waals forces are the electrostatic a ttractions between the electrons in one molecule and the nuclei of an adjacent molecule minus the molecules inter electronic and intemuclear repulsive forces. In about 1930, Fritz London showed that these forces are caused by the attraction between an electric dipole in some molecule and the electric dipole induced in an adjacent one. Therefore, van der Waals forces result from random fluctuations of charge and are important only for molecules that are very close together—in particular, for neighboring molecules. 

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Complexes. The structure of an n a charge-transfer complex between quinoxaline and two iodine atoms has been obtained by X-ray analysis and its thermal stability compared with those of related complexes. The hydrogen bond complex between quinoxaline and phenol has been studied by infrared spectroscopy and compared with many similar complexes. Adducts of quinoxaline with uranium salts and with a variety of copper(II) alkano-ates have been prepared, characterized, and studied with respect to IR spectra or magnetic properties, respectively. 

Esters of a-diazoalkylphosphonic acids (95) show considerable thermal stability but react with acids, dienophiles, and triphenylphosphine to give the expected products. With olefinic compounds in the presence of copper they give cyclopropane derivatives (96), but with no such compounds present vinylphosphonic esters are formed by 1,2-hydrogen shift, or, when this route is not available, products such as (97) or (98) are formed, resulting from insertion of a carbenoid intermediate into C—C or C—H bonds. The related phosphonyl (and phosphoryl) azides (99) add to electron-rich alkynes to give 1,2,3-triazoles, from which the phosphoryl group is readily removed by hydrolysis. 

These may include atomic and molecular hydrogen, as well as hydrogen bonded at oxygen-related clusters. Passivation of the 450°C thermal donors has also been investigated as a function of cluster size by Johnson and Hahn (1986) and Johnson et al. (1986). 

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