Ethylene activation volume

In the study, the kinetic rate constants applicable to the polymerization of ethylene (, ) were used with an assumed activation volume. These values appear to be a reasonably consistent set of constants for the polymerization of ethylene and, as shown... 

A typical unimolecular reaction is the decomposition of organic peroxides for which always positive activation volumes of up to 15 cm3/mol have been observed. The decomposition of di(t-butyl)peroxide, an effective initiator for the high pressure polymerisation of ethylene, into two t-butoxyradicals, exhibits a positive activation volume of 13 cm3/mol (Table 3.2-1, a). When new bonds are formed as in the association... 

In order to investigate the influence of the pressure, polymerization tests were run at pressures of 120 - 190 MPa. As can be seen from Fig. 9.5-6, the rate of polymerization increases from (0.58 to 1.3) 10 3 mol ethylene/(l s). When r, r is plotted on a logarithmic scale versus the pressure, a value of activation volume of -32.5 ml/mol can be evaluated from the slope of the resulting straight line. The negative value is characteristic for polymerization reactions because the volume reduces in the transition state (see Chapter 3.2). 

Solvent effect on rate constants. In this section, the rate constant will be predicted qualitatively in CO2 for the Diels-Alder cycloaddition of isoprene and maleic anhydride, a reaction which has been well-characterized in the liquid state (23,24). In a previous paper, we used E data for phenol blue in ethylene to predict the rate constant of the Menschutkin reaction of tripropylamine and methyliodide (19). The reaction mechanisms are quite different, yet the solvent effect on the rate constant of both reactions can be correlated with E of phenol blue in liquid solvents. The dipole moment increases in the Menschutkin reaction going from the reactant state to the transition state and in phenol blue during electronic excitation, so that the two phenomena are correlated. In the above Diels-Alder reaction, the reaction coordinate is isopolar with a negative activation volume (8,23),... 

From the rate of polymerization rp0j measured at different pressures (Figure 3) an activation volume for the polymerization of ethylene catalyzed by metallocenes can be determined. For this purpose first an overall rate constant kpo] was evaluated from the relation... 

Thermal dimerization of ethylene to cyclobutane is forbidden by orbital symmetry (Sect 3.5 in Chapter Elements of a Chemical Orbital Theory by Inagaki in this volume). The activation barrier is high E =44 kcal mof ) [9]. Cyclobutane cannot be prepared on a preparative scale by the dimerization of ethylenes despite a favorable reaction enthalpy (AH = -19 kcal mol" ). Thermal reactions between alkenes usually proceed via diradical intermediates [10-12]. The process of the diradical formation is the most favored by the HOMO-LUMO interaction (Scheme 25b in chapter Elements of a Chemical Orbital Theory ). The intervention of the diradical intermediates impfies loss of stereochemical integrity. This is a characteric feature of the thermal reactions between alkenes in the delocalization band of the mechanistic spectrum. 

Remarkably, the use of a fluorous biphasic solvent system in combination with a [Rh(NBD)(DPPE)]+-type catalyst (NBD = norbornadiene) copolymerized into a porous nonfluorous ethylene dimethacrylate polymer, resulted in an increased activity of the catalyst relative to a situation when only toluene was used as solvent [30]. The results were explained by assuming that fluorophobicity of the substrate (methyl-trans-cinnamate) leads to a relatively higher local substrate concentration inside the cavities of the polymer when the fluorous solvent is used. That is, the polymer could be viewed as a better solvent than the fluorous solvent system. This interpretation was supported by the observations that (i) the increase in activity correlates linearly with the volume fraction of fluorous solvent (PFMCH) and (ii) the porous ethylene dimethacrylate polymer by itself lowers the concentration of decane in PFMCH from 75 mM to 50 mM, corresponding to a 600 mM local concentration of decane in the polymer. Gas to liquid mass transport limitation of dihydrogen could be mled out as a possible cause. 

Fig. 11. A plot of proton activity pan as a function of electromotive force (mV) for the ethylene glycol-glass electrode at +21°C and — 19°C. The response of the electrode (R ) is given by the slope of the line. The concentration of ethylene glycol is 50% by volume. The points are the experimental results in different buffer systems (a, chloroacetate b, acetate c, cacodylate d, Tris) the straight lines represent ideal behavior.

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