Linear alkanes

We will generate the energies for the carbon-hydrogen bond /fen and the carbon-carbon single bond Hix using the five linear alkanes from ethane through hexane as the five-member data base. The equation to be used is... 

For linear alkanes, the initial fragment lost is an ethyl group (never a methyl group), followed by propyl, butyl, and so on. An intense peak at mass 43 suggests a chain longer than butane. 

Polyethylene. The crystal structure of this polymer is essentially the same as those of linear alkanes containing 20-40 carbon atoms, and the values of Tjj and AHf j are what would be expected on the basis of an extrapolation from data on the alkanes. Since there are no chain substituents or intermolecular forces other than London forces in polyethylene, we shall compare other polymers to it as a reference substance. 

Sulfonation of these compounds produces linear alkane sulfonates (LAS) which are used as biodegradable detergents. 

About 2% of benzene consumed in 1988 was used for the manufacture of straight-chain or branched-chain detergent alkylate. Linear alkane sulfonates (LAS) are widely used as household and laundry detergents. 

Matthews-Akgerman The free-volume approach of Hildebrand was shown to be valid for binary, dilute liquid paraffin mixtures (as well as self-diffusion), consisting of solutes from Cg to Cig and solvents of Cg and C o- The term they referred to as the diffusion volume was simply correlated with the critical volume, as = 0.308 V. We can infer from Table 5-15 that this is approximately related to the volume at the melting point as = 0.945 V, . Their correlation was vahd for diffusion of linear alkanes at temperatures up to 300°C and pressures up to 3.45 MPa. Matthews et al. and Erkey and Akger-man completea similar studies of diffusion of alkanes, restricted to /1-hexadecane and /i-octane, respectively, as the solvents. 

It has already been stated that the evaluation of the non-bonded energy is by far the most time-consuming. Consider a series of calculations of linear alkanes CH3(CH2)n-2CH3. The number of individual contributions to each energy term is given in Table 2.4. 

Catalytic reformers take linear alkanes, e.g., -pentane, and produce branched alkanes, e.g., i-pentane. The catalyst is finely divided platinum on Si203. 

Alkane physisorption on ZSM-22 can be described using an additivity method accounting for the number of carbon atoms inside and outside the ZSM-22 micropores [22]. Linear alkanes can fully enter the micropores while branched alkanes can only enter the pore mouths. Multiple physisorption modes exist at the pore mouths where branched alkanes can enter the pore mouth with each of their straight ends . 

The size of the free space varies slightly as a result of the size and the shape of the molecule to be included. This fact is used in the separation of molecules. A relevant example in petroleum refinement is the separation of paraffins from other compounds with urea. In this case, a channel-like lattice is formed by urea. In the free space linear alkanes (n-octane) find space, whereas branched alkanes (i-octane) cannot be included. 

Fig. 12.4. Vapor-to-water transfer data for saturated hydrocarbons as a function of accessible surface area, from [131]. Standard states are 1M ideal gas and solution phases. Linear alkanes (small dots) are labeled by the number of carbons. Cyclic compounds (large dots) are a = cyclooctane, b = cycloheptane, c = cyclopentane, d = cyclohexane, e = methylcyclopentane, f = methylcyclohexane, g = cA-l,2-dimethylcyclohexane. Branched compounds (circles) are h = isobutane, i = neopentane, j = isopentane, k = neohexane, 1 = isohexane, m = 3-methylpentane, n = 2,4-dimethylpentane, o = isooctane, p = 2,2,5-tri-metbylhexane. Adapted with permission from [74], Copyright 1994, American Chemical Society...

The choice of the solvent has a profound influence over the observed sonochemistry as well. The effect of vapor pressure has already been mentioned. Other liquid properties, such as surface tension and viscosity, will alter the threshold of cavitation (8), but this is generally a minor concern. The chemical reactivity of the solvent is often much more important. As discussed below, aqueous sonochemistry is dominated by secondary reactions of OH- and H- formed from the sonolysis of water vapor in the cavitation zone. No solvent is inert under the high temperature conditions of cavitation even linear alkanes will undergo pyrolytic-like cracking during high intensity sonication (89). One may minimize this... 

When a mixture of diazomethane and H2 was passed over Co, Fe, Ru, Ni or Pd surfaces, a mixture of hydrocarbons was produced (mainly Cj-C18, linear alkanes and monoolefins) whose composition varied with the metal, the temperature and the H2 partial pressure. The close similarity of this product mixture with that ob-... 

The hydroisomerization of heavy linear alkanes is of a great interest in petroleum industry. Indeed, the transformation of long chain n-alkanes into branched alkanes allows to improve the low temperature performances of diesel or lubricating oils [1-3]. On bifunctional Pt-exchanged zeolite catalysts, n-CK, transformed into monobranched isomers, multibranched isomers and cracking products [4], The HBEA zeolite based catalyst was more selective for isomerization than those containing MCM-22 or HZSM-5 zeolites [4], This was explained on one hand by a rapid diffusion of the reaction intermediates inside the large HBEA channels, and on the other hand by the very small crystallites size of this zeolite (0.02 pm). 

The hydroisomerization of linear alkanes nowadays is among the most demanded technologies for transformation of naphtha into high octane gasoline. However, while the processes for hydroisomerization of C4 and C5 - C6 cuts are well established (PENEX, ISOTEX, TIP, HYSOMER, ISOFIN, SKIP, PAR-ISOM), there is no suitable technology for the conversion of longer alkanes (C7 - C8 cuts). 

Fig. 2. Logarithm of the linear alkane. HC , concentration as a function of carbon chain length, n.

Fig. 3. Linear alkane product distribution as obtained in methanol, heptane, and tetrahydrofuran at 300°C with an initial CO/H2 = 1/1 pressure of 100 bar. (Reproducibility of kt/k2 figures not better than 1.)...

At increasing reaction temperatures (230-350°C) the product selectivity is shifted towards C -C. The alkene to alkane ratio declines at higher reaction temperatures whereas the branched to linear alkane ratio increases as well as CO2 formation. These observations are entirely consistent with the behaviour of classical F-T catalysts (Table 1). 

The thermally induced carboxylation of alkanes has been thoroughly investigated by the same group, who have developed a range catalysts, based on vanadium (VO(acac)2) or palladium analogs.22,22a,22b Photochemically induced carbonylation of linear alkanes, to afford aldehydes, is also known (Equation (15)).23,23a... 

Linear alkanes have been hydroxylated in the 2-, 3-, and 4-positions to give secondary alcohols and ketones in the presence of TS-1 catalyst (216,217) with good selectivities based on alkanes and H2O2 (Table XXIV). 

A variety of solid acids besides zeolites have been tested as alkylation catalysts. Sulfated zirconia and related materials have drawn considerable attention because of what was initially thought to be their superacidic nature and their well-demonstrated ability to isomerize short linear alkanes at temperatures below 423 K. Corma et al. (188) compared sulfated zirconia and zeolite BEA at reaction temperatures of 273 and 323 K in isobutane/2-butene alkylation. While BEA catalyzed mainly dimerization at 273 K, the sulfated zirconia exhibited a high selectivity to TMPs. At 323 K, on the other hand, zeolite BEA produced more TMPs than sulfated zirconia, which under these conditions produced mainly cracked products with 65 wt% selectivity. The TMP/DMH ratio was always higher for the sulfated zirconia sample. These distinctive differences in the product distribution were attributed to the much stronger acid sites in sulfated zirconia than in zeolite BEA, but today one would question this suggestion because of evidence that the sulfated zirconia catalyst is not strongly acidic, being active for alkane isomerization because of a combination of acidic character and redox properties that help initiate hydrocarbon conversions (189). The time-on-stream behavior was more favorable for BEA, which deactivated at a lower rate than sulfated zirconia. Whether differences in the adsorption of the feed and product molecules influenced the performance was not discussed. 

The titanosilicate version of UTD-1 has been shown to be an effective catalyst for the oxidation of alkanes, alkenes, and alcohols (77-79) by using peroxides as the oxidant. The large pores of Ti-UTD-1 readily accommodate large molecules such as 2,6-di-ferf-butylphenol (2,6-DTBP). The bulky 2,6-DTBP substrate can be converted to the corresponding quinone with activity and selectivity comparable to the mesoporous catalysts Ti-MCM-41 and Ti-HMS (80), where HMS = hexagonal mesoporous silica. Both Ti-UTD-1 and UTD-1 have also been prepared as oriented thin films via a laser ablation technique (81-85). Continuous UTD-1 membranes with the channels oriented normal to the substrate surface have been employed in a catalytic oxidation-separation process (82). At room temperature, a cyclohexene-ferf-butylhydroperoxide was passed through the membrane and epoxidation products were trapped on the down stream side. The UTD-1 membranes supported on metal frits have also been evaluated for the separation of linear paraffins and aromatics (83). In a model separation of n-hexane and toluene, enhanced permeation of the linear alkane was observed. Oriented UTD-1 films have also been evenly coated on small 3D objects such as glass and metal beads (84, 85). 

Figure 10. Calculated order parameters of the CH2 groups of isolated molecules of linear alkanes with chain length N as indicated, starting from the centre of the molecule towards its end. The ranking number along the chain is indicated by the letter t. MC simulations by Rabinovich and co-workers [74—76]. Copyright (1997) by Elsevier...

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