Cycloalkanes properties

Cycloalkane properties depend on ring size. Strained molecules, i.e., moleeules with distorted geometries, tend to be more reaetive in ring-breaking ehemieal reaetions. For example, eombustion of a strained eyeloalkane should release more energy per CH2 group than eombustion of an unstrained moleeule. 

Toropoy A.A., Nesterov, I.V. and Nabiev, O.M. (2003b) QSPR modeling of cycloalkanes properties by correlation weighting of extended graph valence shells./. Mol. Struct. (Theochem), 637, 37-42. 

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. 

The replacement of carbon by other elements produces changes in several structural parameters and consequently affects the conformational characteristics of the molecule. In this section, we will first describe some stereochemical features of heterocyclic analogs of cycloalkanes. For the purpose of elaborating conformational principles, the discussion will focus on six-membered rings, so that the properties may be considered in the context of a ring system possessing a limited number of low-energy conformations. 

Alicyclic Hydrocarbons. These refer to cyclic analogues of aliphatic hydrocarbons and are named accordingly, using the piefix cyclo-." Their properties are similar to their open-chain aliphatic counterparts. Alicyclic hydrocarbons are subdivided into monocyclic (cycloalkanes, cycloalkenes, cycloalkynes, cycloalkadienes, etc.) and polycyclic aliphatic compounds. Monocyclic aliphatic structures having more than 30 carbon atoms in the ring are known, but those containing 5 or 6 carbon atoms are more commonly found in nature [47, p. 28]. 

Physical properties of cycloalkanes [49, p. 284 50, p. 31] show reasonably gradual changes, but unlike most homologous series, different members exhibit different degrees of chemical reactivity. For example, cyclohexane is the least reactive member in this family, whereas both cyclopropane and cyclobutane are more reactive than cyclopentane. Thus, hydrocarbons containing cyclopentane and cyclohexane rings are quite abundant in nature. 

In a similar way the potential constant method as described here allows the simultaneous vibrational analysis of systems which differ in other strain factors. Furthermore, conformations and enthalpies (and other properties see Section 6.5. for examples) may be calculated with the same force field. For instance, vibrational, conformational, and energetic properties of cyclopentane, cyclohexane and cyclodecane can be analysed simultaneously with a single common force field, despite the fact that these cycloalkanes involve different distributions of angle and torsional strain, and of nonbonded interactions 8, 17). This is not possible by means of conventional vibrational spectroscopic calculations. 

The simple cycloalkanes (CH2)n with n = 5 to 12 are the compounds most frequently studied by force field calculations (8, 9, 11, 12,17, 21). This preference results from their simple structure, from the abundant available experimental material (structural (46), thermo-chemical (47) and vibrational spectroscopic (27, 48, 49) data), and from the fact that, apart from bond length deformations, all other strain factors (angle deformations, unfavourable torsion angles, strongly repulsive nonbonded interactions) are important for the calculation of their properties. The cycloalkanes are thus good candidates for testing force fields. For a more detailed discussion we choose cyclodecane, a so-called medium-ring compound. 

In marked contrast to the n-alkanes, the cycloalkanes exhibit thermodynamic properties where such regularities are no longer present. Heats of formation (AH ) for a substantial number of cycloalkanes are available from heats of combustion. With the exception of cyclohexane, AH°f is always more positive than the quantity — 4.926n. The difference between the two quantities leads to a quantitative assessment of the important notion of ring strain. The AH -values and strain energy data listed in Table 1 were taken from Skinner and Pilcher (1963). Other references give different but usually comparable... 

Perfluorinated alkanes and cycloalkanes are prepared from the corresponding hydrocarbons, either by electrochemical fluorination or by cobalt trifluoride fluo-rination [3], Many perfluorinated solvents are available commercially covering a wide selection of boiling points and densities. Some examples of perfluorinated solvents are listed in Table 3.1 together with their key physical properties. 

One of the most ubiquitous multiple-component contaminants that reaches the soil and deeper subsurface layers is crude oil and its refined products. In the subsurface, these contaminants are transformed differently by various mechanisms (Cozzarelli and Baber 2003). Crude oil contains a multitude of chemical components, each with different physical and chemical properties. As discussed in Chapter 4, the main groups of compounds in crude oils are saturated hydrocarbons (such as normal and branched alkanes and cycloalkanes without double bonds), aromatic hydrocarbons, resins, and asphaltenes, which are high-molecular-weight polycyclic compounds containing nitrogen, sulfur, and oxygen. 

The most intriguing difference between the chemical properties of cyclopolysilanes and those of cycloalkanes is the ability of the former to form either anion or cation radicals upon one-electron reduction or oxidation, respectively. For example, the cyclic pentamer (Mc2Si)5 is reduced to the corresponding radical anion by sodium-potassium alloy in diethyl ether [see eqn (4.1) in Section 4.1.3], whereas the hexamer (Me2Si)6 is oxidised by aluminium trichloride in dichlor-omethane to the corresponding cation radical. In both cases the EPR spectra of the radical ions can be interpreted in terms of a-electron delocalisation over the entire polysilane ring (see Section 10.1.4.1). In this respect, the cyclosilanes resemble aromatic hydrocarbons rather than their aliphatic analogues. 

Alkanes have similar chemical properties, hut their physical properties vary with molecular weight and the shape of the molecule. The low polarity of all the bonds in alkanes means that the only intermolecular forces between molecules of alkanes are the weak dipole-dipole forces (see 2.5.1), which are easily overcome. As a result, compared with other functional groups, alkanes have low melting and boihng points, and low solubility in polar solvents, e.g. water, but high solubility in nonpolar solvents, e.g. hexane and dichloromethane. Most cycloalkanes also have low polarity. 

The cycloalkanes also are known as naphthenes, cycloparaffins, or alicyclic hydrocarbons. In the petroleum industry, this class of hydrocarbons is known as naphthenes. Naphthenes have saturated rings. The general formula for the ring without substituents is CnH2n. This is the same as the general formula for the alkene series however, the structural configurations differ completely and, thus, the physical and chemical properties are not at all similar. 

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