Melting alkanes

Enormous effort is spent on studying complex fluids, more-so than any of the previous topics reviewed above. These fluids include polymer solutions and melts, alkanes, colloidal systems, electrolytes, liquid crystals, micelles, surfactants, dendrimers and, increasingly, biological systems such as DNA and proteins in solution. There are therefore many specialist areas and it is impossible to review them all here. As such, we sample only a select few areas that reflect our own personal interests, and apologise to readers who have specific interests elsewhere. First, we briefly look over some simulations on colloidal systems, alkanes, dendrimers, biomolecular systems, etc, and will then... 

Adams catalyst, platinum oxide, Pt02 H20. Produced by fusion of H2PtCl6 with sodium nitrate at 500-550 C and leaching of the cooled melt with water. Stable in air, activated by hydrogen. Used as a hydrogenation catalyst for converting alkenes to alkanes at low pressure and temperature. Often used on Si02... 

Sen S, Cohen J M, McCoy J D and Curro J G 1994 The structure of a rotational isomeric state alkane melt near a hard wall J Chem. Phys. 101 9010... 

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

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. 

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. 

Polymers have been prepared from nuclear substituted di-(4-hydroxyphenyl)-alkanes, of which the halogenated materials have been of particular interest. The symmetrical tetrachlorobis-phenol A yields a polymer with a glass transition temperature of 180°C and melting range of 250-260°C but soluble in a variety of solvents. 

T. Matsuda, G. D. Smith, R. G. Winkler, D. Y. Yoon. Stochastic dynamics simulations of n-alkane melts confined between solid surfaces Influence of surface properties and comparison with Schetjens-Fleer theory. Macromolecules 28 65- 13, 1995. 

Wojtkonski [185] has also reported on three series of melt spinnable thermotropic aromatic-aliphatic polyimines. The polyimines were prepared by reaction of 1,2-bis(4-formylphenoxy) ethane, terephthalaldehyde, or 4,4 -biphenyldicarboxaldehyde, respectively, with l,n-bis(4-amino-3-methylphenoxy) alkanes where n = 1-10, 12, 14, and 16 in dry DMAC containing 5% dry lithium chloride. The polymers decomposed at 400°C, and as the length of the flexible aliphatic segments increased, melting points decreased. Polymers with an odd... 

LLDPE with narrow molecular weight distribution exhibits a lower, a sharper melting point [3], better hot tack and heat seal properties as well as higher clarity and better impact resistance (Fig. 3), tensile strength (Fig. 4) [11], and lower levels of alkane-soluble components. The most distinguishing characteristic of metallocene-based LLDPEs is that they are not restricted by the current immutable property relationships that are... 

Active Figure 3.4 A plot of melting and boiling points versus number of carbon atoms for the C- -Ci4 alkanes. There is a regular increase with molecular size. Sign in sfwww.thomsonedu.com to see a simulation based on this figure and to take a short quiz. 

Alkanes with long, unbranched chains tend to have higher melting points, boiling points, and enthalpies of vaporization than those of their branched isomers. The difference arises because, compared with unbranched molecules, the atoms of neighboring branched molecules cannot get as close together (Fig. 18.5). As a result, molecules with branched chains have weaker intermolecular forces than their unbranched isomers. 

FIGURE 18.4 The melting and boiling points of the unbranched alkanes from CH4 to C]()H, 4. 

The C=C group and all four atoms attached to it lie in the same plane and are locked into that arrangement by the resistance to twisting of the TT-bond (Fig. 18.7). Because alkene molecules cannot roll up into a ball as compactly as alkanes or rotate into favorable positions, they cannot pack together as closely as alkanes so alkenes have lower melting points than alkanes of similar molar mass. 

Why do branched-chain alkanes have lower melting points and boiling points than unbranched alkanes with the same number of carbon atoms ... 

The double bond in alkenes makes them more rigid than alkanes. Some of the atoms of alkene molecules are locked into a planar arrangement by the TT-bond hence, they cannot roll up into a ball as compactly as alkanes can. Because they do not pack together as compactly as alkanes do, they have lower boiling and melting points. 

The complexes are solids but are not useful as derivatives, since they melt, with decomposition of the complex, at the melting point of urea. They are useful, however, in separating isomers that would be quite difficult to separate otherwise. Thiourea also forms inclusion compounds though with channels of larger diameter, so that n-alkanes cannot be guests but, for example, 2-bromooctane, cyclohexane, and chloroform readily fit. 

Recent and current work along these lines, most of which uses monodis-perse n-alkane melts as the systems of interest, is reviewed here. The implementation of Steps 1-3 for this class of molecules is described first. Then the results obtained by this method for unentangled n-alkane melts are briefly... 

If the diamond lattice itself is used for the mapping of the PE chains, each internal bead represents a methylene unit, the step length is the C-C bond length, and CxH2x 2 is represented by x beads. Typical bulk densities for n-alkane melts, which are in the range 0.7-0.8 g/cm3, are achieved with occupancy of 16-19 % of the sites on this lattice. 

Table 4.7. Periodic boxes employed for simulations of two n-alkane melts [167]... 

For n-alkane melts on the 2nnd lattice, the time for computation of a single MC step scales approximately as N11, where N denotes the number of beads. This exponent was evaluated for simulations with 1500, 2844, and 3950 beads. The exponent for N seems to decrease slightly as N increases it may be closer to 1 for larger systems. 

Dodd, L. R. and Theodorou, D. N. Atomistic Monte Carlo Simulation and Continuum Mean Field Theory of the Structure and Equation of State Properties of Alkane and Polymer Melts. Vol 116,pp, 249-282,... 

IR and Raman spectroscopic studies on films and powders of PDHS indicate that the hexyl side chains are crystallizing into a hydrocarbon type matrix (40). This is indicated by the presence of a number of sharp characteristic alkane bands which become dramatically broadened above the transition temperature. Similar changes are observed for n-hexane below and above the melting point. CPMAS 29Si NMR studies on PDHS also show that the rotational freedom of the side chains increases markedly above the transition temperature (41,42). All of the spectral evidence... 

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