Acetylene data

Vibrational spectroscopy has been, and will continue to be, one of the most important teclmiques in physical chemistry. In fact, the vibrational absorption of a single acetylene molecule on a Cu(lOO) surface was recently reported [ ]. Its endurance is due to the fact that it provides detailed infonnation on structure, dynamics and enviromnent. It is employed in a wide variety of circumstances, from routine analytical applications, to identifying novel (often transient) species, to providing some of the most important data for advancing the understanding of intramolecular and intemiolecular interactions. 

Aryl-S02Cl. At present only a few data concerning electrophilic 1,3-substitution with allenic and acetylenic tin or silicon compounds are available. 

Data for the several flame methods assume an acetylene-nitrous oxide flame residing on a 5- or 10-cm slot burner. The sample is nebulized into a spray chamber placed immediately ahead of the burner. Detection limits are quite dependent on instrument and operating variables, particularly the detector, the fuel and oxidant gases, the slit width, and the method used for background correction and data smoothing. 

The predetonation distance (the distance the decomposition flame travels before it becomes a detonation) depends primarily on the pressure and pipe diameter when acetylene in a long pipe is ignited by a thermal, nonshock source. Figure 2 shows reported experimental data for quiescent, room temperature acetylene in closed, horizontal pipes substantially longer than the predetonation distance (44,46,52,56,58,64,66,67). The predetonation distance may be much less if the gas is in turbulent flow or if the ignition source is a high explosive charge. 

Because it was not possible to explain the differences in the effectiveness of hydrogen as compared to other gases on the basis of differences in their physical properties, ie, thermal conductivity, diffusivity, or heat capacity differences, their chemical properties were explored. To differentiate between the hydrogen atoms in the C2H2 molecules and those injected as the quench, deuterium gas was used as the quench. The data showed that although 90% of the acetylene was recovered, over 99% of the acetylene molecules had exchanged atoms with the deuterium quench to form C2HD and... 

Based on the bench-scale data, two coal-to-acetylene processes were taken to the pilot-plant level. These were the AVCO and Hbls arc-coal processes. The Avco process development centered on identifying fundamental process relationships (29). Preliminary data analysis was simplified by first combining two of three independent variables, power and gas flow, into a single enthalpy term. The variation of the important criteria, specific energy requirements (SER), concentration, and yield with enthalpy are indicated in Figure 12. As the plots show, minimum SER is achieved at an enthalpy of about 5300 kW/(m /s) (2.5 kW/cfm), whereas maximum acetylene concentrations and yield are obtained at about 7400 kW/(m /s) (3.5 kW/cfm). An operating enthalpy between these two values should, therefore, be optimum. Based on the results of this work and the need to demonstrate the process at... 

The economics of the arc-coal process is sensitive to the electric power consumed to produce a kilogram of acetylene. Early plant economic assessments indicated that the arc power consumption (SER = kwh/kgC2H2) must be below 13.2. The coal feedcoal quench experiments yielded a 9.0 SER with data that indicated a further reduction to below 6.0 with certain process improvements. In the propane quench experiment, ethylene as well as acetylene is produced. The combined process SER was 6.2 with a C2H2/C2H4 production ratio of 3 to 2. Economic analysis was completed uti1i2ing the achieved acetylene yields, and an acetylene price approximately 35% lower than the price of ethylene was projected. 

The U.S. Department of Commerce estimates total production of about 163,000 t in 1990. Other estimates based on demand data indicate that it was as high as 175,000 t. With demand and supply in balance, it is estimated that in 1997 the demand will be 185,000 t. The distribution in product demand is projected to be the following 1,4-butanediol and other acetylenic chemicals (45%), vinyl chloride monomer (45%), acetylene black (5%), and industrial use (5%). 

Very Htde data are readily available on China s supply and demand situation. It is known, however, that they rely almost entirely on calcium carbidey for acetylene production and that there are numerous low capacity plants, a situation that is probably not too different from that of Japan. 

Perhaps the most firmly based report for the formation of an azete involves flash pyrolysis of tris(dimethylamino)triazine (303). This gave a red pyrolysate believed to contain the highly stabilized azete (304) on the basis of spectroscopic data. The putative azete decomposed only slowly at room temperature, but all attempts to trap it failed (73AG(E)847). Flash pyrolysis of other 1,2,3-triazines gives only acetylenes and nitriles and it is not possible to tell whether these are formed by direct <,2-l-<,2-l-<,2 fragmentation of the triazine or by prior extrusion of nitrogen and collapse to an azete (81JCR(S)162). 

Electrochemically generated trifluoromethyl radicals add to 1-hexyne to give a 1 4 mixture of ( )- and (Z)-l,l,l-trifluoro-2-heptene [22] Kinetic data on the addition of photochemically generated trifluoromethyl radicals to acetylene and substituted acetylenes were reported [2J]. Alcohols and aldehydes add to hexa-fluoro-2-butyne in the presence of peroxide and y-ray initiation [24] (equations 16 and 17). 

The use of the Hammett equation has also been extended to several new types of applications. Since these are not germane to the subject matter of the present chapter, we wiU simply mention work on applications to ethylenic and acetylenic compounds the various applications to physical properties, such as infrared frequencies and intensities, ultraviolet spectra, polarographic half-wave potentials, dipole moments,NMR and NQR spectra,and solubility data and applications to preparative data and biological activity. 

The data thus obtained allow us to make some generalizations for the heterocy-clization of hydrazides of the vicinal acetylenic derivatives of pyrazolecarboxylic... 

Using a mechanical model and a set of force constants, Popov and Lubuzh (66ZPS498) have calculated vibration frequencies for polyacetylenic groups. But these calculations are rather complex and the data on the IR spectra of acetylenic... 

The high reactivity of monosubstituted acetylenes in many reactions (acetylenic condensation, Favorsky reaction, Mannich reaction, oxidative coupling, etc.) is determined by their acidity (7IMI1 83MI1). The literature data on the thermodynamic CH acidity of these compounds are rather scarce. 

Where do hydrocarbons lie on the acidity scale As the data in Table 8.1 show, both methane (pKa 60) and ethylene (plC, = 44) are very weak acids and thus do not react with any of the common bases. Acetylene, however, has piCa = 25 and can be deprotonated by the conjugate base of any acid whose pKa is greater than 25. Amide ion (NH2-), for example, the conjugate base of ammonia (pKa - 35), is often used to aeprotonate terminal aikynes. 

Long-range coupling between protons more than two carbon atoms apart is sometimes observed when v bonds intervene. An example is found in l-methoxy-l-buten-3-yne. Not only does the acetylenic proton, Ha, couple with the vinylic proton H, it also couples with the vinylic proton Hc, four carbon atoms away. The data are ... 

Acetylene, clathrate in hydroquinone, 7 hydrate thermodynamic data and lattice constants, 8 Acrylamides, polymerization of, 181 Acrylonitrile, 155 Activity coefficients, 125... 

Methods of EGA using selective sorption, condensation of effluent gases, infrared absorption and thermoparticulate analysis have been reviewed by Lodding [144]. The use of simple gas burette systems should not be forgotten and an Orsat gas analysis apparatus can provide useful measurements in studies of the decomposition of formates [169]. Problems have been encountered in the determination of water released Kiss et al. [170—172] have measured the formation of this compound from infrared analyses of the acetylene evolved following reaction of water with calcium carbide. Kinetic data may be obtained by wet methods ammonia, determined by titration after absorption in an aqueous solution, has been used to measure a—time values for the decomposition of ammonium salts in a fluidized bed [173],... 

Data are also available with a-acetylenic aliphatic sulphones, which involve only two steps i.e., saturation of the triple bond without subsequent cleavage of the Caliphalic—S bond, since it is not reactive. However, the introduction of an aromatic ring to the S02 group does not lead, contrary to what is observed with enones, to a potential shift toward less reducing potential values. Thus, the aromatic moiety introduced apparently does not bring any additional conjugation effect but even seems to decrease the activation of the unsaturated bond, as shown by data in Tables 6 and 7 where most of the potentials refer to the same saturated calomel electrode under similar experimental conditions. 

Figure 7. Characteristic dependencies of fractional intensities of several prominent ions on the pressure of acetylene in the source chamber of the spectrometer. To avoid confusion, only the smooth curves through the data points are presented...

In low pressure flames, however, the situation is less clear cut (9). For example, in stoichiometric acetylene-oxygen flames at 1.0 torr (T = 2500°K.) the value of k required to explain the experimental data can be calculated by equating the rate of OH - formation at the steady state to the appropriate loss rate, which must include diffusion ... 

We shall find it convenient to divide the data sets for substituent effects at carbon—carbon triple bonds into three categories acetylene, ethynylene, and reactions at carbon—carbon triple-bond sets. 

Data are extant in the literature for five sets of substituted acetylene dipole moments. The correlation of dipole moments with the Hammett equation was discussed in section II.A.l. of this work. The application of the Hammett equation to dipole moments of acetylenes was first reported by Charton (18). The sets studied here are reported in Table XXXIII. Results of the correlations are presented in Table XXXIV, and values of Pr are set forth in Table XXXV. 

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