Propane method

In the case of butadiene, the calculation of the number of connections by the "propane method" gives ri = 6 (connections), distributed in two groups one of four equivalent substrucUires and another group of two equivalent substructures. Therefore,... 

Similarly, for the p-benzoquinone the "propane method" gives an index of complexity of r = 22, distributed in two groups of eight equivalent substructures and three groups of two equivalent substructures each. 

Buono and coworkers developed a platinum analog of their Pd-catalyzed cyclo-propanation method (Section 9.4.3). Their new catalyst, Pt(r] -acetato)- [(R)(Ph) P0]2H, was successfully applied to reactions of heteroatom-containing alkenes [57]. 

More than 5 million tons of acrylonitrile are made annually. It is synthesized industrially by the gas-phase heterogeneous ammoxidation of propene. New catalysts based on Bi-Mo or V-Sb oxides may lead to manufacture of this important compound from propane. Although the new process has a considerably lower selectivity to acrylonitrile, the lower cost of the alkane makes it economically interesting (the propane method can cut at least 20 % from the production costs of the propene route). Nevertheless, increases in the selectivity of the catalysts, especially at higher conversions, will be necessary for this process to compete with the usual process of acrylonitrile synthesis [24]. 

From Diazo-compounds. The routine cuprous-catalysed diazomethane cyclo-propanation method has been used on bicyclic and bridged olefins. With fneso-tetraphenylporphin, this procedure gave a single cyclopropane product, unlike the corresponding reaction with diazo-esters. Trishomobenzene has been prepared by multiple use of this diazomethane method. It was shown to be the trans-isomer (78) by n.m.r. spectroscopy in (78) there are seven types of H whereas in its cis-isomer there would be only three. Twelve isomeric products have been isolated by preparative g.l.c. from the reaction of diazomethane-Cu2Cl2 with biallenyl (79). Some of the products could be synthesized independently, otherwise structural assignments were based upon spectroscopic evidence. 

Where the distance to the customer is very large, or where a gas pipeline would have to cross too many countries, gas may be shipped as a liquid. Gas has to be chilled to -160°C in a LNG plant to keep it in liquid form, and is shipped in refrigerated tankers. To condition the gas for liquefaction any COj, HjS, water and heavier hydrocarbons must be removed, by the methods already discussed. The choice of how much propane and butane to leave in the LNG depends upon the heating requirements negotiated with the customer. 

A variant on this procedure produces a first approximation to the molecular mechanics (MM) heat paiameters (Chapters 4 and 5) for C—C and C—H. Instead of atomization energies, the enthalpies of formation of propane and butane (—25.02 and —30.02 kcal mol ) are put directly into the b vector. The results (2.51 kcal mol and —3.76 kcal mol ) are not very good approximations to the heat parameters actually used (2.45 kcal mol and —4.59 kcal mol ) because of other factors to be taken up later, but the calculation illustrates the method and there is rough agreement. 

In the above reaction one molecular proportion of sodium ethoxide is employed this is Michael s original method for conducting the reaction, which is reversible and particularly so under these conditions, and in certain circumstances may lead to apparently abnormal results. With smaller amounts of sodium alkoxide (1/5 mol or so the so-called catal3rtic method) or in the presence of secondary amines, the equilibrium is usually more on the side of the adduct, and good yields of adducts are frequently obtained. An example of the Michael addition of the latter type is to be found in the formation of ethyl propane-1 1 3 3 tetracarboxylate (II) from formaldehyde and ethyl malonate in the presence of diethylamine. Ethyl methylene-malonate (I) is formed intermediately by the simple Knoevenagel reaction and this Is followed by the Michael addition. Acid hydrolysis of (II) gives glutaric acid (III). 

This method is merely an application of the Grignard reaction but is a lot less troublesome because it uses really common chemicals. This method can be done as it was done in the reference where a phenylbutene was made using a bromopropane ( bromo-propane and bromoethane are cheap to purchase or can be made... 

The main problem in this technique is getting the atoms into the vapour phase, bearing in mind the typically low volatility of many materials to be analysed. The method used is to spray, in a very fine mist, a liquid molecular sample containing the atom concerned into a high-temperature flame. Air mixed with coal gas, propane or acetylene, or nitrous oxide mixed with acetylene, produce flames in the temperature range 2100 K to 3200 K, the higher temperature being necessary for such refractory elements as Al, Si, V, Ti and Be. 

Specifications for the principal LPG products are summarized in Table 4. Detailed specifications and test methods for LPG are pubHshed by the Gas Processor s Association (GPA) (3) and ASTM (4). The ASTM specification for special-duty propane and GPA specification for propane HD-5 apply to propane that is intended primarily for engine fuel. Because most domestic U.S. LPG is handled through copper tubing, which could fail if corroded, all products must pass the copper strip corrosion test. A test value of No. 1 represents a LPG noncorrosive to the copper. 

Low temperature filtration (qv) is a common final refining step to remove paraffin wax in order to lower the pour point of the oil (14). As an alternative to traditional filtration aided by a propane or methyl ethyl ketone solvent, catalytic hydrodewaxing cracks the wax molecules which are then removed as lower boiling products. Finished lubricating oils are then made by blending these refined stocks to the desired viscosity, followed by introducing additives needed to provide the required performance. Table 3 Usts properties of typical commercial petroleum oils. Methods for measuring these properties are available from the ASTM (10). 

The only method utilized commercially is vapor-phase nitration of propane, although methane (70), ethane, and butane also can be nitrated quite readily. The data in Table 5 show the typical distribution of nitroparaffins obtained from the nitration of propane with nitric acid at different temperatures (71). Nitrogen dioxide can be used for nitration, but its low boiling point (21°C) limits its effectiveness, except at increased pressure. Nitrogen pentoxide is a powerful nitrating agent for alkanes however, it is expensive and often gives polynitrated products. 

Other potential synthetic methods include fermentation (qv) of certain carbohydrates (qv), oxidation of propane, hydrogenation of acetone, and hydrolysis of isopropyl acetate. The hydrogenation of by-product acetone is the only method practiced commercially. 

Another method of manufacturing SiC by the decomposition of a gas mixture containing silane, propane, and hydrogen, and hydrogen chloride has been described (80). With such a mixture, it was possible to work at a relatively lower (1200°C) temperature and it was claimed that compact, homogeneous P SiC crystals were obtained. In a variation of this gas-phase synthesis theme, SiC has been produced from the reaction of SiCl and methane (81). SiC precipitates from 1000 to 3000°C. 

Oxidation of Hydrocarbons. Ethanol is one of a variety of oxygen-containing compounds produced by the oxidation of hydrocarbons. Ethanol is reported to be obtained in a yield of 51% by the slow combustion of ethane (158,159). When propane is oxidi2ed at 350°C under a pressure of 17.2 MPa (170 atm) (160,161), 8% of the oxygen is converted to ethanol. Lower conversions to ethanol are obtained by oxidi2ing butane. Other oxidation systems used to produce ethanol and acetaldehyde (162—164) and methods for separating the products have been described in the patent Hterature. 

Dehydrogenation. The dehydrogenation of paraffins is equihbrium-limited and hence requites high temperatures. Using this approach and conventional separation methods, both Houdry and UOP have commercialized the dehydrogenation of propane to propylene (92). A similar concept is possible for ethane dehydrogenation, but an economically attractive commercial reactor has not been built. 

In an analogous fashion the oxidative coupling of 1,3-diselenols is used for the preparation of 1,2-diselenolanes, the precursors being obtained by a variety of methods (see Chapter 4.35). Similar reaction s have been used for the preparation of 1,2-thiaselenolanes. Substituted propane-1,3-diselenones (287) are oxidized by halogen to the corresponding 3,5-diamino-l,2-diselenolylium chloride (288) (67AJC1991). 

EPA Method 25A is the instrumental analyzer method for determination of total gaseous organic concentration using a flame ionization analyzer. The method apphes to the measurement of total gaseous organic concentration of vapors consisting primarily of alkanes, alkenes, and/or arenes (aromatic hydrocarbons). The concentration is expressed in terms of propane (or other appropriate organic calibration gas) or in terms or carrion. 

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

The example provided in Table 2 is for a four eomponent mixture of hydroearbons (methane, ethane, propane, and n-oetane). The weighting method is a eommon ealeulation procedure that proeess engineers will encounter many times. Computations for simple systems can be easily set up on an Exeel spreadsheet. 

Product Characteristics Propane Butane Mixtures HD-5 Methods Cr ... 

The reaction of chlorodifluorotnethane with alkoxide ions generated in low concentration from halide ions and epoxides [28, 29] is an interesting, higher temperature method that gives good to excellent yields of gem-difluorocyclo-propanes from just moderately nucleophilic olefins (equation 9)... 

The use of Figure 9.2 requires that liquid propane s temperature relative to its boiling point and superheat-limit temperature be known. Table 6.1 gives these temperatures T, = 231 K, and T j = 326 K. It is obvious that the liquid temperature can easily rise above the superheat-limit temperature when the vessel is exposed to a fire. Therefore, the explosively flashing-liquid method must be selected. The... 

Thus, the BLEVE of a tank truck filled with propane can cause window pane breakage up to a distance of about 100 m. Note that, with this method of calculating distance of a given overpressure, one or two iterations may be necessary. The number of iterations will be higher when the distance for a given impulse is sought, or when the refined method is used. 

The calculation method can be selected by application of the decision tree in Figure 9.2. The liquid temperature is believed to be about 339 K, which is the temperature equivalent to the relief valve set pressure. The superheat limit temperatures of propane and butane, the constituents of LPG, can be found in Table 6.1. For propane, T, = 326 K, and for butane, T i = 377 K. The figure specifies that, if the liquid is above its critical superheat limit temperature, the explosively flashing liquid method must be chosen. However, because the temperature of the LPG is below the superheat limit temperature (T i) for butane and above it for propane, it is uncertain whether the liquid will flash. Therefore, the calculation will first be performed with the inclusion of vapor energy only, then with the combined energy of vapor and liquid. 

For a molecule as simple as Fl2, it is hard to see much difference between the valence bond and molecular orbital methods. The most important differences appear- in molecules with more than two atoms. In those cases, the valence bond method continues to view a molecule as a collection of bonds between connected atoms. The molecular- orbital method, however, leads to a picture in which the sane electron can be associated with many, or even all, of the atoms in a molecule. We ll have more to say about the similarities and differences in valence bond and molecular- orbital theory as we continue to develop their principles, beginning with the simplest alkanes methane, ethane, and propane. 

Like propane, butanes are obtained from natural gas liquids and from refinery gas streams. The C4 acyclic paraffin consists of two isomers n-butane and isobutane (2-methylpropane). The physical as well as the chemical properties of the two isomers are quite different due to structural differences, for example, the vapor pressure (Reid method) for n-butane is 52 Ib/in., while it is 71 Ib/in. for isobutane. This makes the former a more favorable gasoline additive to adjust its vapor pressure. However, this use is declining in the United States due to new regulations that reduce the volatility of gasolines to 9 psi, primarily by removing butane. ... 

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