Branched n-alkanes

In binary mixtures of branched n-alkanes x is obtained by substitution of the general expression of in eqn (3.102) ... 

Let us first consider the vibrational spectra (infrared) of IPP in the melt (Figure 3-9a) [74], In this physical state, polymer chains possess a conformationally irregular structure like any liquid branched n-alkane. We expect the infrared spectrum to consist of relatively few bands easily identified as the group frequencies of CH3 and CH2 and CH groups. Other modes may be identified with caution, but their location is irrelevant to the present discussion. The experimental infrared spectrum of Figure 3-9a is in full agreement with the expectations. 

Branched-chain alkanes, also known as isoparaffins or isoalkanes, are possible when n > 4. The prefix iso is used when two methyl groups are attached to a terminal carbon atom of an otherwise straight chain and the prefix neo when three methyl groups are attached in that manner. Branched-chain alkanes are sometimes regarded as normal alkanes with attached substituent alkyl groups. An example is... 

Normal alkanes (n-alkanes, n-paraffms) are straight-chain hydrocarbons having no branches. Branched alkanes are saturated hydrocarbons with an alkyl substituent or a side branch from the main chain. A branched... 

The molecular ions decrease in intensity with increasing chain length but are still detectable at C40. In contrast to branched alkanes, the loss of a methyl group is not favored for n-alkanes. Usually the... 

The effective cross-section of an /z-alkane molecule is smaller than 5 A the effective cross-section of branched, cyclic, or aromatic hydrocarbon molecules is larger than 5 A. Therefore only n-alkanes are adsorbed by a 5-A zeolite all other types of hydrocarbons are excluded. The adsorbed n-alkanes can be recovered by different methods and are subsequently available in a pure form, for further processing. 

The separation of n-alkanes from a kerosene or gas oil fraction by a molecular sieve can be performed in a liquid phase or in a gas phase process. In the gas phase processes there are no problems of cleaning the loaded molecular sieve from adherent branched and cyclic hydrocarbons. However, the high reaction temperature of the gas phase processes leads to the development of coke-contaminated sieves, which have to be regenerated from time to time by a careful burning off of the coke deposits. 

The biodegradation of n-alkanes and the pathways whereby it is accomplished are well established. The range of componnds includes branched-chain compounds such as pristane... 

As further subfractionation facilitates subsequent studies at a molecular level, further separation into compound groups is applied. For example, the saturated hydrocarbon fraction can be treated with 5 A molecular sieves or urea for the removal of n-alkanes, leaving behind a fraction of branched and cyclic alkanes [7,8]. The procedure is described in the following text in detail. 

Molecular Sieve 5A n-Alkanes and other straight-chain molecules in the presence of branched chain molecules. 

Thiourea canal inclusion compounds 19 26) have a wider diameter than those formed by urea, such that n-alkanes are not included but that molecules of cross-section approximately 5.8-6.8 A are trapped 64). Thus many inclusion compounds have been reported between thiourea and branched alkanes or cyclic molecules. Of special interest are the inclusion compounds with cyclohexane derivatives and the recent studies carried out on the preferred conformation(s) of the ring in the restricted environment of the thiourea canal. 

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). 

Only large-pore zeolites exhibit sufficient activity and selectivity for the alkylation reaction. Chu and Chester (119) found ZSM-5, a typical medium-pore zeolite, to be inactive under typical alkylation conditions. This observation was explained by diffusion limitations in the pores. Corma et al. (126) tested HZSM-5 and HMCM-22 samples at 323 K, finding that the ZSM-5 exhibited a very low activity with a rapid and complete deactivation and produced mainly dimethyl-hexanes and dimethylhexenes. The authors claimed that alkylation takes place mainly at the external surface of the zeolite, whereas dimerization, which is less sterically demanding, proceeds within the pore system. Weitkamp and Jacobs (170) found ZSM-5 and ZSM-11 to be active at temperatures above 423 K. The product distribution was very different from that of a typical alkylate it contained much more cracked products trimethylpentanes were absent and considerable amounts of monomethyl isomers, n-alkanes, and cyclic hydrocarbons were present. This behavior was explained by steric restrictions that prevented the formation of highly branched carbenium ions. Reactions with the less branched or non-branched carbenium ions require higher activation energies, so that higher temperatures are necessary. 

Susceptibility to n-alkane degradation is an inverse function of chain length. Branched alkanes are less susceptible than straight-chain n-alkanes, and the most resilient saturated components are the pristine and phytane isoprenoids (Wang et al. 1998). 

The GPC of a local crude (Bryan, Texas) sample spiked with a known mixture of n-alkanes and aromatics is shown in Figure 5 and the GPC of the crude is shown in Figure 6. The hydrocarbon mixture is used to calibrate the length of the species which separates as a function of retention volume. Ttie molecular length is expressed as n-alkane carboa units although n-alkanes represent only a fraction of the hydrocarbons in the crude. In addition to n-alkanes, petroleum crude is composed of major classes of hydrocarbons such as branched and cyclic alkanes, branched and cyclic olefins and various aromatics and nonvolatiles namely asphaltenes. Almost all of the known aromatics without side chains elute after n-hexane (Cg). If the aromatics have long side chains, the linear molecular size increases and the retention volume is reduced. Cyclic alkanes have retention volumes similar to those of aromatics. GPC separates crude on the basis of linear molecular size and the species are spread over 10 to 20 ml retention volume range and almost all of the species are smaller than the polystyrene standard (37A). In other words, the crude has very little asphaltenes. The linear... 

GC of fraction 7 (Figure 5" I) has alkanes as small as The ratio of peak heights of pristane to C. increases in the uC of this fraction compared to previous fractions as expected from its shorter linear molecular size. The smaller peaks between n-alkane peaks are alkylated phenols and branched alkanes. 

Alkane elimination has a low yield during the photolysis of liquid n-alkanes (e.g., n-pentane [104,106]). This reaction takes place with high yield only for branched alkanes where it is likely to be a main primary-decomposition step [105,107]. 

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