Hydrogen bonding vapor phase

Dyke T R 1984 Microwave and radiofrequency spectra of hydrogen-bonded complexes in the vapor phase Topics in Current Chemistry 120 85-113... 

Catalytic hydrogenation of furan to tetrahydrofuran is accompHshed in either Hquid or vapor phase. Hydrogenation of the double bonds is essentially quantitative over nickel catalysts but is generally accompanied by hydrogenolysis over the noble metals. 

In the vapor phase formic acid forms a hydrogen-bonded dimer ... 

Finally, selective hydrogenation of the olefinic bond in mesityl oxide is conducted over a fixed-bed catalyst in either the Hquid or vapor phase. In the hquid phase the reaction takes place at 150°C and 0.69 MPa, in the vapor phase the reaction can be conducted at atmospheric pressure and temperatures of 150—170°C. The reaction is highly exothermic and yields 8.37 kJ/mol (65). To prevent temperature mnaways and obtain high selectivity, the conversion per pass is limited in the Hquid phase, and in the vapor phase inert gases often are used to dilute the reactants. The catalysts employed in both vapor- and Hquid-phase processes include nickel (66—76), palladium (77—79), copper (80,81), and rhodium hydride complexes (82). Complete conversion of mesityl oxide can be obtained at selectivities of 95—98%. 

Reaction Mechanism. High temperature vapor-phase chlorination of propylene [115-07-17 is a free-radical mechanism in which substitution of an allyhc hydrogen is favored over addition of chlorine to the double bond. Abstraction of allyhc hydrogen is especially favored since the allyl radical intermediate is stabilized by resonance between two symmetrical stmctures, both of which lead to allyl chloride. 

Dioxolane also pseudorotates essentially freely in the vapor phase. 2,2 -Bi-l,3-dioxolane (128) has been shown by X-ray crystallography to have a conformation midway between the half-chair and envelope forms. The related compound 2-oxo-l 3-dioxolane (129) shows a half-chair conformation. This result is confirmed by microwave spectroscopy and by NMR data. Analysis of the AA BB NMR spectra of the ring hydrogen atoms in some 1,3-dioxolane lerivatives is in agreement with a puckered ring. Some 2-alkoxy-l,3-dioxolanes (130) display anti and gauche forms about the exocyclic C(2)—O bond. 

Beyer, A., Karpfen, A., and Schuster, P. Energy Surfaces of Hydrogen-Bonded Complexes in the Vapor Phase. 120, 1-40 (1984). 

Glycerol is well known for its strong hydrogen bonding in the liquid phase and its high viscosity. To study its wetting properties, we deposited glycerol on mica by condensation from its vapor in standard laboratory air [9]. 

A molecular perspective reveals why energy must be supplied to boil water. A molecule of water cannot escape the liquid phase unless it has enough energy of motion to overcome the hydrogen bonding forces that hold liquid water together. About 40 kJ of heat must be supplied to transfer 1 mol of water molecules from the liquid phase into the vapor phase. 

Another mechanism for alkanone-sensitized photodehydrochlorination comprises Norrish type I scission of the ketone, followed by ground-state reactions of radicals (19). However, the evidence for such a mechanism is based on experiments that were carried out in the vapor phase (19). Initiation of the photodegradation of PVC by hexachloroacetone has been suggested to involve the abstraction of hydrogen from the polymer by radicals resulting from the photolysis of the ketone s carbon-chlorine bonds (22). 

Both types of hydrogen bonds occur in pure liquids as well as in solutions. Many substances are associated at least partially in the vapor phase as a result of hydrogen bonding. For example, hydrogen cyanide is associated to give structures such as... 

The weaker the intermolecular forces between molecules in the liquid phase, the higher is the vapor pressure. Generally, hydrogen bonding and the cumulative dispersion forces in larger molecules are the most significant factors (see Table 13-3). In order of decreasing vapor pressure,... 

FIG. 3 The vapor phase water dimer structure. Polar covalent bonds are shown as solid lines and the hydrogen bond as a dashed line (adapted from Ludwig, 2001). 

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