Butane stabilities

Lythgoe and co-workers synthesized azoxymethane and other azoxyalkanes. The photolysis of azoxymethane led to a decomposition to give nitrogen, nitrous oxide, methane, and ethane (Scheme 47)."° Azoxy-t-butane stabilized by t-butyl groups, however, resulted in the formation of 1,3-di-t-butyloxadiaziridine upon UV irradiation at 10°C (Scheme 48). "... 

Alkyl substituents stabilize a carbonyl group m much the same way that they sta bilize carbon-carbon double bonds and carbocations—by releasing electrons to sp hybridized carbon Thus as then heats of combustion reveal the ketone 2 butanone is more stable than its aldehyde isomer butanal... 

The alkanes have low reactivities as compared to other hydrocarbons. Much alkane chemistry involves free-radical chain reactions that occur under vigorous conditions, eg, combustion and pyrolysis. Isobutane exhibits a different chemical behavior than / -butane, owing in part to the presence of a tertiary carbon atom and to the stability of the associated free radical. 

Bicyclo[1.1.0]butane is an example of a molecule in which severe angle strain results in decreased stability and greatly enhanced reactivity. The bicyclo[1.1.0]butane ring has a strain energy of 63.9kcal/mol, and the central bond is associated with a relatively high... 

A gas-processing plant, as described in Chapter 9, is designed to recover ethane, propane, butane, and other natural gas liquids from the gas stream. A condensate stabilizer also recovers some portion of these liquids. The colder the temperature of the gas leaving the overhead condenser in a reflux stabilizer, or the colder the feed stream in a cold-feed stabilizer, and the higher the pressure in the tower, the greater the recovery of these components as liquids. Indeed, any stabilization process that leads to recovery of more molecules in the final liquid product is removing those molecules from the gas stream. In this sense, a stabilizer may be considered as a simple form of a gas-processing plant. 

Absorber oil then flows to a still where it is heated to a high enough temperature to drive the propanes, butanes, pentanes and other natural gas liquid components to the overhead. The still is similar to a crude oil stabilizer with reflux. The closer the bottom temperature approaches the boiling temperature of the lean oil the purer the lean oil which will be recirculated to the absorber. Temperature control on the condenser keeps lean oil from being lost with the overhead. 

Butanes are chosen as the simplest models for the normal and branched isomers. Both branched and normal isomers contain a C-C bond (2 ) interacting with the terminal C-H bonds (2 and 2 ) (Scheme 26a). The cyclic -aj-a2 -a3 a2- interaction (Scheme 26b) occurs in the polarization of the middle C-C a-bond by the interactions with the antiperiplanar C-H a-bonds. The orbital phase is continuous in the branched isomer and discontinuous in the normal isomer (cf Scheme 4). The branched isomer is more stable. The basic rule of the branching effects on the stability of alkanes is ... 

The number (nj) of the cross ct conjugations of the trios of a C-C bond and two antiperiplanar C-H bonds is important for the stabilities of alkanes. The cross conjugation number (nj) of an alkane is defined as that of the conformer where the longest C-C chain has trans a zigzag structure. For example, there are three cross conjugations (n = 3) in isobutene and none in n-butane (n = 0) (Scheme 27). Isobutane is more stable than n-butane [34, 35]. 

The bond between the bridgehead carbons of bicyclo[1.1.0]butanes can be either normal or inverted [35]. The normal bond is stabilized by the high s-character (Scheme 16a). In this case, the hybrids on the bridgeheads Y have low s-character for the bridging Y-X bonds. Electronegative atoms X or substituents R at Y stabilize... 

The best fit of velocity exponent n in Hp °c ug (Figure 4.3.11) for pure propane (n-butane) is n = 4.733 (3.638), corresponding to Sc = 1.37 (1.61) from n = (2Sc-l)/ (Sc -1), which agreed well with the suggested value of Sc = 1.376 (1.524). The experimental liftoff height data are shown in Figure 4.3.12 for various nozzle diameters and partial air dilutions to fuel [53]. It can be observed that the air dilution to fuel does not alter Ypst and S° sf The results substantiated the role of tri-brachial flames on flame stabilization in laminar jets. As mentioned previously. Equation 4.3.5 limits the maximum velocity Ug for Sc > 1, which corresponds to blowout condition. 

Figure 8.7. Steam reforming of n-butane as a function of time for a conventional Ni catalyst and a novel Ni-Au alloy catalyst, showing the superior stability ofthe latter. [Adapted from...

Activity in n-butane isomerization reaction of various alkaline salts of H3PW12O40 and H4SiWi2O40 was shown to be strongly dependent on the strength and number of accessible protons whereas the stability with time on stream was correlated to the presence of mesoporosity. For the liquid iC4/C4 continuous alkylation reaction, the strength and the number of acid sites appeared less important than the existence of mesoporosity indicating that the diffusion of the reactants and of the products plays an important role in this reaction. 

The proline-catalyzed reaction has been extend to the reaction of propanal, butanal, and pentanal with a number of aromatic aldehydes and proceeds with high syn selectivity.197 The reaction can also be carried out under conditions in which the imine is formed in situ. Under these conditions, the conjugative stabilization of the aryl imines leads to the preference for the aryl imine to act as the electrophile. A good yield of the expected P-aminoalcohol was obtained with propanal serving as both the nucleophilic and the electrophilic component. The product was isolated as a 7-amino alcohol after reduction with NaBH4. 

For many years, butadiene has been manufactured by dehydrogenating butene or butane over a catalyst at appropriate combinations of temperature and pressure. It is customary to dilute the butene feed with steam (10-20 moles H20/mole butene) to stabilize the temperature during the endothermic reaction and to help shift the equilibrium conversion in the desired direction by reducing the partial pressures of hydrogen and butadiene. The current processes suffer from two major disadvantages. 

Chiral diphosphites based on (2R,3R)-butane-2,3-diol, (2R,4R)-pentane-2,4-diol, (25, 5S)-hexane-2,5-diol, (lS -diphenylpropane-hS-diol, and tV-benzyltartarimide as chiral bridges have been used in the Rh-catalyzed asymmetric hydroformylation of styrene. Enantioselectivities up to 76%, at 50% conversion, have been obtained with stable hydridorhodium diphosphite catalysts. The solution structures of [RhH(L)(CO)2] complexes have been studied NMR and IR spectroscopic data revealed fluxional behavior. Depending on the structure of the bridge, the diphosphite adopts equatorial-equatorial or equatorial-axial coordination to the rhodium. The structure and the stability of the catalysts play a role in the asymmetric induction.218... 

The effect of an applied pressure on the UCFT has been investigated for polymer particles that are sterically stabilized by polyisobutylene and dispersed in 2-methy1-butane. It was observed that the UCFT was shifted to a higher temperature as the hydrostatic pressure applied to the system increased. There was also a qualitative correlation between the UCFT as a function of applied pressure and the 6 conditions of PIB + 2-methylbutane in (P,T) space. These results can be rationalized by considering the effect of pressure on the free volume dissimilarity contribution to the free energy of close approach of interacting particles. Application of corresponding states concepts to the theory of steric stabilization enables a qualitative prediction of the observed stability behaviour as a function of temperature and pressure. 

A breakthrough in hydro formylation was achieved with the introduction of a tri-arylphosphine-modified, in particular triphenylphosphine-modified, rhodium catalyst. [5] This innovation provided simultaneous improvements in catalyst stability, reaction rate and process selectivity. Additionally, products could be separated from catalyst under hydro formylation conditions. One variant is described as Gas Recycle (Figure 2.1) since the products are isolated from the catalyst by vaporization with a large recycle of the reactant gases. [6] The recycle gas is chilled to condense butanals. 

In this equation the —225.7 1.3 kJ mol 1 is the hydrogenation enthalpy of 1,3-butadiene to n-butane. This last expression speaks to substituent/diene interactions and to substituent-substituent interactions. Both electronic and steric effects contribute. Again, this allows calibration of a substituted diene with 1,3-butadiene itself. A positive sign can be interpreted as the substituted species being more stabilized than the archetype. 

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