Alkane points

Key properties of noble gases are summarized in Table 1 other properties are in refs. 6 and 11. The formation and detection of M-Ng bonds provide many of the same challenges as for transition metal-alkane bonds. Comparison of spectra and energetics of species such as Cr(CO)5Xe and Cr(CO)s(alkane) points to further similarities in bond enthalpies. Recent reviews tackle complexes of alkanes in detail . Since investigations of alkane complexes are more frequent than those of xenon complexes, we may use these results to anticipate the formation of further M-Ng bonds [e.g., to HMn(CO)4]. 

Their boiling points and densities are higher than alkanes having the same number of carbon atoms. 

Paraffins consist mainly of straight chain alkanes, with a very small proportion of isoalkanes and cycloalkanes. Their freezing point is generally between 30°C and 70°C, the average molecular weight being around 350. When present, aromatics appear only in trace quantities. 

We will return to the orbital hybridization model to discuss bonding m other aliphatic hydrocarbons—alkenes and alkynes—later m the chapter At this point how ever we 11 turn our attention to alkanes to examine them as a class m more detail... 

An alkyl group lacks one of the hydrogens of an alkane A methyl group (CH3 —) is an alkyl group derived from methane (CH4) Unbranched alkyl groups m which the point of attachment is at the end of the chain are named m lUPAC nomenclature by replac mg the ane endings of Table 2 2 by yl... 

An additional feature of lUPAC nomenclature that concerns the direction of num bermg is the first point of difference rule Consider the two directions m which the following alkane may be numbered... 

FIGURE 2 12 Boiling points of unbranched alkanes and their 2 methyl branched iso mers (Temperatures in this text are expressed in de grees Celsius C The SI unit of temperature is the kelvin K To convert degrees Celsius to kelvins add 273 15 )... 

As noted earlier m this section branched alkanes have lower boiling points than their unbranched isomers Isomers have of course the same number of atoms and elec Irons but a molecule of a branched alkane has a smaller surface area than an unbranched one The extended shape of an unbranched alkane permits more points of contact for mtermolecular associations Compare the boiling points of pentane and its isomers... 

Match the boiling points with the appropriate alkanes Alkanes octane 2 methylheptane 2 2 3 3 tetramethylbutane nonane foiling points °C 1 atm) 106 116 126 151 ... 

Alkanes and cycloalkanes are nonpolar and insoluble m water The forces of attraction between alkane molecules are induced dipole/induced dipole attractive forces The boiling points of alkanes increase as the number of carbon atoms increases Branched alkanes have lower boiling points than their unbranched isomers There is a limit to how closely two molecules can approach each other which is given by the sum of their van der Waals radii... 

We have seen in this chapter that among isomenc alkanes the unbranched isomer is the least stable and has the highest boiling point the most branched isomer is the most stable and has the lowest boiling point Does this mean that one alkane boils lower than another because it is more stable" Explain... 

In this chapter we explored the three dimensional shapes of alkanes and cycloalkanes The most important point to be taken from the chapter is that a molecule adopts the shape that minimizes its total strain The sources of strain m alkanes and cycloalkanes are... 

Boiling Point When describing the effect of alkane structure on boiling point m Sec tion 2 17 we pointed out that van der Waals attractive forces between neutral molecules are of three types The first two involve induced dipoles and are often referred to as dis persion forces or London forces... 

Table 4 2 lists the boiling points of some representative alkyl halides and alcohols When comparing the boiling points of related compounds as a function of the alkyl group we find that the boiling point increases with the number of carbon atoms as it does with alkanes... 

The procedures to be described m the remainder of this chapter use either an alkane or an alcohol as the starting material for preparing an alkyl halide By knowing how to prepare alkyl halides we can better appreciate the material m later chapters where alkyl halides figure prominently m key chemical transformations The preparation of alkyl halides also serves as a focal point to develop the principles of reaction mechanisms... 

Alkynes resemble alkanes and aUcenes m their physical properties They share with these other hydrocarbons the properties of low density and low water solubility They are slightly more polar and generally have slightly higher boiling points than the corre spondmg alkanes and alkenes... 

At this point It s useful to compare some structural features of alkanes alkenes and alkynes Table 9 1 gives some of the most fundamental ones To summarize as we progress through the series m the order ethane ethylene acetylene... 

The physical properties (boiling point solubility m water dipole moment) of alkynes resemble those of alkanes and alkenes... 

Some classes of compounds are so prone to fragmentation that the molecular ion peak IS very weak The base peak m most unbranched alkanes for example is m/z 43 which IS followed by peaks of decreasing intensity at m/z values of 57 71 85 and so on These peaks correspond to cleavage of each possible carbon-carbon bond m the mol ecule This pattern is evident m the mass spectrum of decane depicted m Figure 13 42 The points of cleavage are indicated m the following diagram... 

It IS instructive to compare the physical properties of ethers with alkanes and alcohols With respect to boiling point ethers resemble alkanes more than alcohols With respect to solubility m water the reverse is true ethers resemble alcohols more than alkanes Why" ... 

Systematic names for carboxylic acids are derived by counting the number of car bons m the longest continuous chain that includes the carboxyl group and replacing the e ending of the corresponding alkane by oic acid The first three acids m Table 19 1 methanoic (1 carbon) ethanoic (2 carbons) and octadecanoic acid (18 carbons) illus trate this point When substituents are present their locations are identified by number... 

Hydrogen bonding m carboxylic acids raises their melting points and boiling points above those of comparably constituted alkanes alcohols aldehydes and ketones... 

Section 20 8 Esters are polar and have higher boiling points than alkanes of compa rable size and shape Esters don t form hydrogen bonds to other ester molecules so have lower boiling points than analogous alcohols They can form hydrogen bonds to water and so are comparable to alcohols m their solubility m water... 

We have often seen that the polar nature of a substance can affect physical properties such as boiling point This is true for amines which are more polar than alkanes but less polar than alcohols For similarly constituted compounds alkylamines have boiling points higher than those of alkanes but lower than those of alcohols... 

Cation (Section 1 2) Positively charged ion Cellobiose (Section 25 14) A disacchande in which two glu cose units are joined by a 3(1 4) linkage Cellobiose is oh tamed by the hydrolysis of cellulose Cellulose (Section 25 15) A polysaccharide in which thou sands of glucose units are joined by 3(1 4) linkages Center of symmetry (Section 7 3) A point in the center of a structure located so that a line drawn from it to any element of the structure when extended an equal distance in the op posite direction encounters an identical element Benzene for example has a center of symmetry Cham reaction (Section 4 17) Reaction mechanism m which a sequence of individual steps repeats itself many times usu ally because a reactive intermediate consumed m one step is regenerated m a subsequent step The halogenation of alkanes is a chain reaction proceeding via free radical intermediates... 

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. 

Alkan olamines have high boiling points and under normal ambient conditions their vapor pressures are low. Only DMAMP (see Table 2) forms an azeotrope with water, which boils at 98.4°C and contains 25% by weight of DMAMP. According to current DOT regulations, AMP, AMP-95, DMAMP, DMAMP-80, AEPD, and AB are all classified as combustible Hquids. 

A paraffin wax is a petroleum wax consisting principally of normal alkanes. MicrocrystalHne wax is a petroleum wax containing substantial proportions of branched and cycHc saturated hydrocarbons, in addition to normal alkanes. SernimicrocrystaUine wax contains more branched and cycHc compounds than paraffin wax, but less than microcrystalHne. A classification system based on the refractive index of the wax and its congealing point as... 

Paraffin wax is macrocrystalline, britde, and is composed of 40—90 wt % normal alkanes, with the remainder C g—isoalkanes and cycloalkanes. Paraffin wax has Httle affinity for oil content fully refined paraffin has less than 1 wt % cmde scale, 1—2 wt %, and slack [64742-61-6] above 2 wt %. Within these classes, the melting point of the wax determines the actual grade, with a range of about 46—71°C. Typical properties of petroleum waxes are listed in Table 3. 

Pentaerythritol with its four primary hydroxyl groups is used for the preparation of tetraesters and presents Httie difficulty except for its high melting point of 263°C, when pure. Pentaerythritol tetraesters are used in aircraft lubes, synthetic drying oils, and alkyds. Esters derived from trimethylo1 alkanes and dipentaerythritol are also used in alkyd resins (qv). Esterification may take place in situ during preparation of the alkyd. 

Heats of Vapon a/ion andFusion. A simple linear summation of most of the Lyderson groups (187) has been proposed for heat of vaporization at the normal boiling point and heat of fusion at atmospheric pressure for a wide variety of organic compounds (188). Average errors of 1.2 and 4.3% for group contribution-based estimations of heats of vaporization for selected n- and iso-alkanes, respectively, have been reported (215). 

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. 

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