Hydrogen expansion

W.F. Baade, G.D. Snyder, and J.M. Abrardo, Generating Hydrogen for New Reformulated Gasoline and Clean Diesel Requirements, Low Cost Hydrogen Expansion Without Increased NO, SO, emissions. Hydrocarbon Processing. Martyn V. Twigg, Catalyst Handbook, 2nd ed., Wolfe Publishing, Ltd., London (1989). 

Joule-Thomson effect Most gases cool down while expanding (process of decompression). However, hydrogen stored at a temperature exceeding the inverse temperature (r > Tin = 193 K) is heated upon expansion. For example, at hydrogen expansion from 20 to 0.1 MPa the temperature rise is 6-8 K. 

Example 5.14. A normal hydrogen expansion engine operates between an inlet pressure of 1.52 MPa and an exhaust pressure of 0.101 MPa. If the efficiency of the expansion engine is 80 % and the actual temperature measured at the exhaust is 40 K, what is the inlet temperature ... 

With 2-methyl- and 2,4-dimethylthiazole, the methyl thiirenium ion (m/e 72) is obtained, which can easily lose a hydrogen radical to give the ml ell ion (confirmed by the metastable peak). This latter can rearrange by ring expansion to give the thietenyl cation whose structure was confirmed in certain spectra by the presence of a metastable peak corresponding to the decomposition of the m/e 71 ion to give the thioformyl cation m/e 45, probably by elimination of acetylene. 

Figure 9.46 shows an example of a fluorescence excitation spectmm of hydrogen bonded dimers of x-tetrazine (1,2,4,5-tetraazabenzene). The pressure of x-tetrazine seeded into helium carrier gas at 4 atm pressure was about 0.001 atm. Expansion was through a 100 pm diameter nozzle. A high-resolution (0.005 cm ) dye laser crossed the supersonic jet 5 mm downstream from the nozzle. 

Expansion from high to low pressures at room temperature cools most gases. Hydrogen is an exception in that it heats upon expansion at room temperature. Only below the inversion temperature, which is a function of pressure, does hydrogen cool upon expansion. Values of the Joule-Thorns on expansion coefficients for hydrogen have been tabulated up to 253 MPa (36,700 psi) (48), and the Joule-Thorns on inversion curve for i7n -hydrogen has been determined (49,50). 

Upon melting, ice loses its open structure with the "melting" of some fraction of the hydrogen bonds, and so the volume of the Hquid water decreases, reaching a minimum at 4°C above this temperature thermal expansion dominates the density. 

Maltol. Otsuka Chemical Co. in Japan has operated several electroorganic processes on a small commercial scale. It has used plate and frame and aimular cells at currents in the range of 4500—6000 A (133). The process for the synthesis of maltol [118-71 -8], a food additive and flavor enhancer, starts from furfural [98-01-1] (see Food additives Flavors and spices). The electrochemical step is the oxidation of a-methylfurfural to give a cycHc acetal. The remaining reaction sequence is acid-catalyzed ring expansion, epoxidation with hydrogen peroxide, and then acid-catalyzed rearrangement to yield maltol, ie ... 

The mass spectrum of 2-pyrone shows an abundant molecular ion and a very prominent ion due to loss of CO and formation of the furan radical cation. Loss of CO from 4-pyrone, on the other hand, is almost negligible, and the retro-Diels-Alder fragmentation pathway dominates. In alkyl-substituted 2-pyrones loss of CO is followed by loss of a hydrogen atom from the alkyl substituent and ring expansion of the resultant cation to the very stable pyrylium cation. Similar trends are observed with the benzo analogues of the pyrones, although in some cases both modes of fragmentation are observed. Thus, coumarins. 

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