Dependent on Molecular Size

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. 

The two constants kj and k describe exactly the same kind of diffusional processes and differ only in direction. Hence they have the same dependence on molecular size, whatever that might be, and that dependence therefore cancels out. 

Rysee, H. J. P. a membrane effect of basic polymers dependent on molecular size. Nature 1967. 215, 934—936. 

Parameters r, q and q are pure component molecular-structure constants depending on molecular size and external surface areas. For fluids other than water or lower alcohols, q = q. ... 

The first factor k. 1 = 35, is expected to be temperature dependent via an Arrhenius fjfpe relationship the second factor defines functionality dependence on molecular size the third factor indicates that smaller molecules are more likely to react than larger species, perhaps due to steric hindrance potentials and molecular mobility. The last term expresses a bulk diffusional effect on the inherent reactivity of all polymeric species. The specific constants were obtained by reducing a least squares objective function for the cure at 60°C. Representative data are presented by Figure 5. The fit was good. 

The fourth type of mechanism is exclusion although perhaps inclusion would be a better description. Strictly, it is not a true sorption process as the separating solutes remain in the mobile phase throughout. Separations occur because of variations in the extent to which the solute molecules can diffuse through an inert but porous stationary phase. This is normally a gel structure which has a small pore size and into which small molecules up to a certain critical size can diffuse. Molecules larger than the critical size are excluded from the gel and move unhindered through the column or layer whilst smaller ones are retarded to an extent dependent on molecular size. 

These techniques are of particular interest in that they provide a means of separating molecular species which are difficult to separate by other techniques and which may be present in very low concentrations. Such species include large molecules, sub-micrometre size particles, stereo-isomers and the products from bioreactors (Volume 3). The separations can be highly specific and may depend on molecular size and shape, and the configuration of the constituent chemical groups of the molecules. 

Figure 4.2. Variation of heat capacity with temperature as calculated from the equations of Frenkel et al. [4]. The differences observed between isotopic species and the way heat capacity depends on molecular size and structure can be described thermodynamically, but they must be explained by the methods of quantum-statistical thermodynamics. The right-hand scale is for H2 and D2 the left-hand scale is for the other compounds.

The distribution of a-, P- and y-CDs is highly dependent on the origin of biocatalyst used (See section on Cyclodextrin Glucanotransferases). Product distributions maybe altered by the addition of specific precipitants, such as aromatics and long chain alcohols 9, 20), Depending on molecular size, these precipitants preferentially complex with specific CD species and are removed from solution. 

Compounds can cross biological membranes by two passive processes, transcellu-lar and paracellular mechanisms. For transcellular diffusion two potential mechanisms exist. The compound can distribute into the lipid core of the membrane and diffuse within the membrane to the basolateral side. Alternatively, the solute may diffuse across the apical cell membrane and enter the cytoplasm before exiting across the basolateral membrane. Because both processes involve diffusion through the lipid core of the membrane the physicochemistry of the compound is important. Paracellular absorption involves the passage of the compound through the aqueous-filled pores. Clearly in principle many compounds can be absorbed by this route but the process is invariably slower than the transcellular route (surface area of pores versus surface area of the membrane) and is very dependent on molecular size due to the finite dimensions of the aqueous pores. 

Use of the differential refractometer detector is applicable to all polymers having refractive indices different from that of the solvent. However, a correction must be made if the polymer refractive index depends on molecular size, such as at very low molecular weights. 

Because of Ihis striking dependence on molecular size, the measurement of molecular weight and dimensions is very important. Some of the... 

Collect intensity data (1000-100 000 data points depending on molecular size). 

The efficiency of this proposed process may depend on molecular size, molecular shape, charge and chemical properties of the molecule. This may account for the fact that linear polyhydroxyl compounds, (e.g. sorbitol, mannitol) do not stabilize to the same extent as the cyclic molecule inositol. 

CGE offers an alternative that provides fast separations, quantitative analysis, and automated operation. High-level sensitivity detection (500 ng/mL protein) is possible with this technique.22 Compounds such as nucleic acids and SDS-protein complexes that possess the same mass-to-charge ratios cannot be resolved by CZE. To separate these species, electrophoresis must be performed in a medium in which the rate of migration depends on molecular size. CGE is useful for these separations. A material such as... 

Multipurpouse use None Depending on molecular size Concentrated in a waste stream Some Highly effective... 

Intrapellet transport restrictions can limit the rate of removal of products, lead to concentration gradients within pellets, and prevent equilibrium between the intrapellet liquid and the interpellet gas phase. Transport restrictions increase the intrapellet fugacity of hydrocarbon products and provide a greater chemical potential driving force for secondary reactions. The rate of secondary reactions cannot be enhanced by a liquid phase that merely increases the solubility and the local concentration of a reacting molecule. Olefin fugacities are identical in any phases present in thermodynamic equilibrium thus, a liquid phase can only increase the rate of a secondary reaction if it imposes a transport restriction on the removal of reacting species involved in such a reaction (4,5,44). Intrapellet transport rates and residence times depend on molecular size, just as convective transport and bed residence time depend on space velocity. As a result, bed residence time and molecular size affect chain termination probability and paraffin content in a similar manner. 

The diffusion-enhanced olefin readsorption model described in Section III,C was used to predict the effect of carbon number on chain growth probability and paraffin selectivity. The model requires only one adjustable parameter the exponent c in a hydrocarbon diffusivity equation that depends on molecular size ( ), but that is identical for paraffins and olefins of equal size ... 

Giant molecules zeolites de-ionized" water., Temporary hardness and permanent hardness methods of softening water. Heat capacity (specific heat). Van der Waals attraction, boiling point, melting point-dependence on molecular size. Electric dipole moments of molecules—effect on boiling point. Ionic dissocia-... 

Factor Xa inhibitors vary in their efficacy to inhibit factor Xa depending on molecular size, access to clot bound fector Xa, access to prothrombinase bound factor Xa, specificity and kinetics of inhibition. It is probably the inhibition of clot bound fector Xa that relates to the prolongation of the aPTT as observed with some of the fector Xa inhibitors and, therefore, the inability to inhibit clot bound factor Xa that relates to a lack of aPTT prolongation by other agents. DX-9065a with a relatively lower molecular weight may be more effective in the inhibition of clot bound fector Xa than TAP or pentasaccharide. 

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