Hydrocarbon representations

Extensive discussions have focused on the conformation of the alkyl chains in the interior ". It has been has demonstrated that the alkyl chains of micellised surfactant are not fully extended. Starting from the headgroup, the first two or three carbon-carbon bonds are usually trans, whereas gauche conformations are likely to be encountered near the centre of tlie chain ". As a result, the methyl termini of the surfactant molecules can be located near the surface of the micelle, and have even been suggested to be able to protrude into the aqueous phase "". They are definitely not all gathered in the centre of tire micelle as is often suggested in pictorial representations. NMR studies have indicated that the hydrocarbon chains in a micelle are highly mobile, comparable to the mobility of a liquid alkane ... 

MMl, MM2, MM3, and MM4 are general-purpose organic force fields. There have been many variants of the original methods, particularly MM2. MMl is seldom used since the newer versions show measurable improvements. The MM3 method is probably one of the most accurate ways of modeling hydrocarbons. At the time of this book s publication, the MM4 method was still too new to allow any broad generalization about the results. However, the initial published results are encouraging. These are some of the most widely used force fields due to the accuracy of representation of organic molecules. MMX and MM+ are variations on MM2. These force fields use five to six valence terms, one of which is an electrostatic term and one to nine cross terms. 

Two-Dimensional Representation of Chemical Structures. The lUPAC standardization of organic nomenclature allows automatic translation of a chemical s name into its chemical stmcture, or, conversely, the naming of a compound based on its stmcture. The chemical formula for a compound can be translated into its stmcture once a set of semantic rules for representation are estabUshed (26). The semantic rules and their appHcation have been described (27,28). The inverse problem, generating correct names from chemical stmctures, has been addressed (28) and explored for the specific case of naming condensed benzenoid hydrocarbons (29,30). 

Fig. 12. A, Schematic representation of parallel arrays of polynuclear aromatic hydrocarbon molecules in a mesophase sphere. B, a) isolated mesophasc spheres in an isotropic fluid pitch matrix b) coalescence of mesophase c) structure of semi-coke after phase inversion and solidification.

The meaning of the word aromaticity has evolved as understanding of the special properties of benzene and other aromatic molecules has deepened. Originally, aromaticity was associated with a special chemical reactivity. The aromatic hydrocarbons were considered to be those unsaturated systems that underwent substitution reactions in preference to addition. Later, the idea of special stability became more important. Benzene can be shown to be much lower in enthalpy than predicted by summation of the normal bond energies for the C=C, C—C, and C—H bonds in the Kekule representation of benzene. Aromaticity is now generally associated with this property of special stability of certain completely conjugated cyclic molecules. A major contribution to the stability of aromatic systems results from the delocalization of electrons in these molecules. 

The case study has documented the investigation and root cause analysis process applied to the hydrocarbon explosion that initiated the Piper Alpha incident. The case study serves to illustrate the use of the STEP technique, which provides a clear graphical representation of the agents and events involved in the incident process. The case study also demonstrates the identification of the critical events in the sequence which significantly influenced the outcome of the incident. Finally the root causes of these critical events were determined. This allows the analyst to evaluate why they occurred and indicated areas to be addressed in developing effechve error reduchon strategies. 

Fig. 2. Schematic representation of selected hydrocarbon chains in the crystalline and the amorphous regions of polyethylene, respectively. For ensembles of chains uniformly distributed around the dashed lines the deuterons from planar and conical distributions as indicated...

Fig. 39. Graphical representation of the correlation between i> (cm ) for Ni(ol) and the energy (E ) of the ir orbital of the free olefin. The olefins are lettered as in Table XVI. Squares indicate hydrocarbon olefins, and circles, fluoro- or chloro-olefins (141).

Explicit mechanisms attempt to include all nonmethane hydrocarbons believed present in the system with an explicit representation of their known chemical reactions. Atmospheric simulation experiments with controlled NMHC concentrations can be used to develop explicit mechanisms. Examples of these are Leone and Seinfeld (164), Hough (165) and Atkinson et al (169). Rate constants for homogeneous (gas-phase) reactions and photolytic processes are fairly well established for many NMHC. Most of the lower alkanes and alkenes have been extensively studied, and the reactions of the higher family members, although little studied, should be comparable to the lower members of the family. Terpenes and aromatic hydrocarbons, on the other hand, are still inadequately understood, in spite of considerable experimental effort. Parameterization of NMHC chemistry results when NMHC s known to be present in the atmosphere are not explicitly incorporated into the mechanism, but rather are assigned to augment the concentration of NMHC s of similar chemical nature which the... 

Tarek et al. [388] studied a system with some similarities to the work of Bocker et al. described earlier—a monolayer of n-tetradecyltrimethylammonium bromide. They also used explicit representations of the water molecules in a slab orientation, with the mono-layer on either side, in a molecular dynamics simulation. Their goal was to model more disordered, liquid states, so they chose two larger molecular areas, 0.45 and 0.67 nm molecule Density profiles normal to the interface were calculated and compared to neutron reflectivity data, with good agreement reported. The hydrocarbon chains were seen as highly disordered, and the diffusion was seen at both areas, with a factor of about 2.5 increase from the smaller molecular area to the larger area. They report no evidence of a tendency for the chains to aggregate into ordered islands, so perhaps this work can be seen as a realistic computer simulation depiction of a monolayer in an LE state. 

Figure 41-3. Diagrammatic representation of a phospholipid or other membrane lipid. The polar head group is hydrophilic, and the hydrocarbon tails are hydrophobic or lipophilic. The fatty acids in the tails are saturated (S) or unsaturated (U) the former are usually attached to carbon 1 of glycerol and the latter to carbon 2. Note the kink in the tail of the unsaturated fatty acid (U), which is important in conferring increased membrane fluidity.

Figure 9.6. Schematic representation of the catalytic cycle for the hydrodesulfurization of a sulfur-containing hydrocarbon (ethane thiol) by a sulfur vacancy on M0S2 The C2H5SH molecule adsorbs with its sulfur atom towards...

FIGURE 12.4 (A) Diagrammatic representation of the separation of major simple lipid classes on silica gel TLC — solvent system hexane diethylether formic acid (80 20 2) (CE = cholesteryl esters, WE = wax esters, HC = hydrocarbon, EEA = free fatty acids, TG = triacylglycerol, CHO = cholesterol, DG = diacylglycerol, PL = phospholipids and other complex lipids). (B) Diagrammatic representation of the separation of major phospholipids on silica gel TLC — solvent sytem chloroform methanol water (70 30 3) (PA = phosphatidic acid, PE = phosphatidylethanolamine, PS = phosphatidylserine, PC = phosphatidylcholine, SPM = sphingomyelin, LPC = Lysophosphatidylcholine). 

The pulse technique may also be conveniently extended to include stages of reactant preparation. Figure 9 shows a schematic representation of a pulse reactor system recently used by Gault et al. (81), which includes stages for alcohol (the reactant precursor) dehydration and subsequent olefin hydrogenation, the resulting saturated hydrocarbon being the material of catalytic interest. A method has been described (82) which allows the use of a pulse reactor at above atmospheric pressure. 

Fig. 3.5 Representation of a scheme of an experiment (upper set of drawings) and the obtained experimental results presented as AFM images (middle part) and cross-sectional profiles (bottom) that provides evidence of silica nucleation and shell formation on biopolymer macromolecules. Scheme of experiment. This includes the following main steps. 1. Protection of the mica surface against silica precipitation. It was covered with a fatty (ara-chidic) acid monolayer transferred from a water substrate with the Langmuir-Blodgett technique. This made the mica surface hydrophobic because of the orientation of the acid molecules with their hydrocarbon chains pointing outwards. 2. Adsorption of carbohydrate macromolecules. Hydrophobically modified cationic hydroxyethylcellulose was adsorbed from an aqueous solution. Hydrocarbon chains of polysaccharide served as anchors to fix the biomacromolecules firmly onto the acid monolayer. 3. Surface treatment by silica precursor. The mica covered with an acid mono-...

Finally, we have designed and synthesized a series of block copolymer surfactants for C02 applications. It was anticipated that these materials would self-assemble in a C02 continuous phase to form micelles with a C02-phobic core and a C02-philic corona. For example, fluorocarbon-hydrocarbon block copolymers of PFOA and PS were synthesized utilizing controlled free radical methods [104]. Small angle neutron scattering studies have demonstrated that block copolymers of this type do indeed self-assemble in solution to form multimolecular micelles [117]. Figure 5 depicts a schematic representation of the micelles formed by these amphiphilic diblock copolymers in C02. Another block copolymer which has proven useful in the stabilization of colloidal particles is the siloxane based stabilizer PS-fr-PDMS [118,119]. Chemical... 

Figure 2 A possible representation of the Menger micelle in which the hydrocarbon tails are extended. Counterions are not shown. (From Ref. 2 with permission.)...

Time scaling may not be applicable to halogenated hydrocarbons as blood concentrations of these chemicals do not increase as exposure time is increased beyond 5-10 min (Bakshi et al. 1998). In the Utell et al. (1997) study with human volunteers exposed to HCFC-141b, the relationship between exposure concentration and blood level was linear and reached equilibrium at 250 ppm within 145 min. Graphical representation of the exposure time-blood concentration indicated that at the higher concentrations, equilibrium was approached at 225 min, and at 55 min concentrations were within 80% of the 225 min concentration. Furthermore, the circulating HCFC-141b concentration, rather than duration of exposure, defines whether or not a cardiac response will occur. 

Whether or not our representation of the non-ionic chain-carrier as an ester is correct, the balance between the ionic and non-ionic forms for the system styrene—perchloric acid—methylene dichloride seems to be very delicate. Since the enthalpy terms affecting this balance must be small, and the entropy terms are likely to be important, it is not possible at present to analyse the situation in detail. However it is predictable that the factors which would favour the ionic form, as against the ester, are lower ionization potential of the hydrocarbon radical, weaker ester bond, more polar solvent, and lower temperature. 

Fig. 1 Schematic representation of a globular micelle O, hydrophilic head group VvV, hydrocarbon tail...

The so-called unsaturated properties of benzene and other hydrocarbons, their ability to "soak up" more hydrogen, for example, resulted in cartoonlike graphic representations for the valence bond.80 Thus ... 

FIGURE 6.2 Representation of multivariate data by icons, faces, and music for human cluster analysis and classification in a demo example with mass spectra. Mass spectra have first been transformed by modulo-14 summation (see Section 7.4.4) and from the resulting 14 variables, 8 variables with maximum variance have been selected and scaled to integer values between 1 and 5. A, typical pattern for aromatic hydrocarbons B, typical pattern for alkanes C, typical pattern for alkenes 1 and 2, unknowns (2-methyl-heptane and meta-xylene). The 5x8 data matrix has been used to draw faces (by function faces in the R-library Tea-chingDemos ), segment icons (by R-function stars ), and to create small melodies (Varmuza 1986). Both unknowns can be easily assigned to the correct class by all three representations. 

Reaction (3.1) is the initiation step, where M is a reactant molecule forming a radical R. Reaction (3.2) is a particular representation of a collection of propagation steps and chain branching to the extent that the overall chain branching ratio can be represented as a. M is another reactant molecule and a has any value greater than 1. Reaction (3.3) is a particular chain propagating step forming a product R It will be shown in later discussions of the hydrocarbon-air... 

At temperatures around 300-400°C and slightly higher, explosive reactions in hydrocarbon-air mixtures can take place. Thus, explosion limits exist in hydrocarbon oxidation. A general representation of the explosion limits of hydrocarbons is shown in Fig. 3.9. 

Weisman, W. 1998. Analysis of Petroleum Hydrocarbons in Environmental Media. Total Petroleum Hydrocarbons Criteria Working Group Series, Vol. 1. Amherst Scientific Publishers, Amherst, MA.(See also Vol. 2, Composition of Petroleum Mixtures, 1998 Vol. 3, Selection of Representation Total Petroleum Hydrocarbons Fractions Based on Fate and Transport Considerations, 1997 Vol. 4, Development of Fraction-Specific Reference Doses and Reference Concentrations for Total Petroleum Hydrocarbons, 1997 and Vol. 5, Human Health Risk-Based Evaluation of Petroleum Contaminated Sites, Implementation of the Working Group Approach, 1999.)... 

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