Molecular homologous series

One of the most sensitive tests of the dependence of chemical reactivity on the size of the reacting molecules is the comparison of the rates of reaction for compounds which are members of a homologous series with different chain lengths. Studies by Flory and others on the rates of esterification and saponification of esters were the first investigations conducted to clarify the dependence of reactivity on molecular size. The rate constants for these reactions are observed to converge quite rapidly to a constant value which is independent of molecular size, after an initial dependence on molecular size for small molecules. The effect is reminiscent of the discussion on the uniqueness of end groups in connection with Example 1.1. In the esterification of carboxylic acids, for example, the rate constants are different for acetic, propionic, and butyric acids, but constant for carboxyUc acids with 4-18 carbon atoms. This observation on nonpolymeric compounds has been generalized to apply to polymerization reactions as well. The latter are subject to several complications which are not involved in the study of simple model compounds, but when these complications are properly considered, the independence of reactivity on molecular size has been repeatedly verified. 

Some substances are odorous, others are not. Humans can smell at a distance if one smells the roses in a garden, it is not ordinarUy considered that part of the rose is in contact with the nose. Substances of different chemical constitution may have similar odors. Substances of similar constitution usuaUy have similar odors, eg, in a homologous series nevertheless, even stereoisomers may have different odors. Substances of high molecular weight are usuaUy inodorous and often nonvolatile and insoluble. The quaUty as weU as the strength of odor may change on dUution. 

The ability of C to catenate (i.e. to form bonds to itself in compounds) is nowhere better illustrated than in the compounds it forms with H. Hydrocarbons occur in great variety in petroleum deposits and elsewhere, and form various homologous series in which the C atoms are linked into chains, branched chains and rings. The study of these compounds and their derivatives forms the subject of organic chemistry and is fully discussed in the many textbooks and treatises on that subject. The matter is further considered on p. 374 in relation to the much smaller ability of other Group 14 elements to form such catenated compounds. Methane, CH4, is the archetype of tetrahedral coordination in molecular compounds some of its properties are listed in Table 8.4 where they are compared with those of the... 

Bruhl found that the increase of CHj in all the homologous series of fatty compounds corresponds to a difierence of 4 57 in the molecular refraction for the red hydrogen line. By deducting n times this value from the molecular refraction cf an aldehyde or ketone of the formula C H2 0, he found 2 328 to be the value for intra-radical oxygen. Similarly the values of other groupings have been determined which may be summarised as follows —... 

Where FCl is the solute gas-liquid partition coefficient, r is the tendency of the solvent to interact through k- and n-electron pairs (Lewis basicity), s the contribution from dipole-dipole and dipole-induced dipole interactions (in molecular solvents), a is the hydrogen bond basicity of the solvent, b is its hydrogen bond acidity and I is how well the solvent will separate members of a homologous series, with contributions from solvent cavity formation and dispersion interactions. 

The effect of surfactant structures and properties on emulsion polymerization have been investigated by numerous authors [82-89]. Efforts were made to study the effects of surfactants with different molecular weights on the rate of polymerization [82], swelling and solubilization effects [83], effects of alkyl chain length of homologous series on the rate of polymerization, particle size... 

Zugenmaier and Heiske [60] presented the crystal and molecular structures of the homologous series of 4 -(hydroxy-l-n-alkoxy)-4-cyanobi-phenyls (CBO(CH2)nOH) n = 4, 5, 7-11). The chemical structure of the compounds is shown in Fig. 1. All compounds of the series exhibit a nematic phase. The crystal and molecular data of the investigated compounds CBO(CH2)nOH and some derivatives are presented in Table 3. 

FIGURE 6 Molecular structures of poIy(CTTE), poly(CTTH), and poly(CTTP), a homologous series of tyrosine-derived polymers used in a study of the effect of the C-terminus protecting group on the materials properties of the resulting polymers. Cbz" stands for the benzyloxycarbonyl group (47). 

The descriptors used should not be highly collinear with each other, for two reasons. First, this can lead to statistical instability and overprediction, and second, collinearity makes mechanistic interpretation difficult. For example, Cronin and Schultz [41] have pointed out that although a good correlation could be obtained between the skin sensitization potential and the hydrophobicity of a series of bromoalkanes, a correlation between skin sensitization potential and molecular weight had exactly the same statistics, because hydrophobicity and molecular weight are very highly correlated in homologous series. 

With the exception of rather small polar molecules, the majority of compounds, including drugs, appear to penetrate biological membranes via a lipid route. As a result, the membrane permeability of most compounds is dependent on K0/w. The physicochemical interpretation of this general relationship is based on the atomic and molecular forces to which the solute molecules are exposed in the aqueous and lipid phases. Thus, the ability of a compound to partition from an aqueous to a lipid phase of a membrane involves the balance between solute-water and solute-membrane intermolecular forces. If the attractive forces of the solute-water interaction are greater than those of the solute-membrane interaction, membrane permeability will be relatively poor and vice versa. In examining the permeability of a homologous series of compounds... 

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