Arrhenius parameters for

TABLE 8.1 The acidity dependence and Arrhenius parameters for the nitration of some cations in... 

In a senes of papers. Tedder and co-workers reported the factors determining the reactivity of perfluormated radicals with various fluoroethylenes Relative Arrhenius parameters for tnfluoromethyl radicals [17] and pentafluoroethyl radicals [/5] were determined, with higher selectivity demonstrated for the higher homologue Selectivity of addition to unsymmetncal olefins was found also to increase with greater radical branching [19]... 

The reaction between nitroxides and carbon-centered radicals occurs at near (but not at) diffusion controlled rates. Rate constants and Arrhenius parameters for coupling of nitroxides and various carbon-centered radicals have been determined.508 311 The rate constants (20 °C) for the reaction of TEMPO with primary, secondary and tertiary alkyl and benzyl radicals are 1.2, 1.0, 0.8 and 0.5x109 M 1 s 1 respectively. The corresponding rate constants for reaction of 115 are slightly higher. If due allowance is made for the afore-mentioned sensitivity to radical structure510 and some dependence on reaction conditions,511 the reaction can be applied as a clock reaction to estimate rate constants for reactions between carbon-centered radicals and monomers504 506"07312 or other substrates.20... 

Viswanadhan and Matticc278 carried out calculations aimed at rationalizing the relative frequency of backbiting in these and other polymerizations in terms of the ease of adopting the required conformation for intramolecular abstraction (see 2.4.4), More recent theoretical studies generally support these conclusions and provide more quantitative estimates of the Arrhenius parameters for the... 

Fig. 16. Graphical representation of Arrhenius parameters for the low temperature decomposition of ammonium perchlorate (pelleted, orthorhombic, o, and cubic, , forms). Compensation behaviour is observed. Data from Jacobs and Ng [452]. N = nucleation, B = branching, G = growth processes.

Powell and Searcy [1288], in a study of CaMg(C03)2 decomposition at 750—900 K by the torsion—effusion and torsion—Langmuir techniques, conclude that dolomite and C02 are in equilibrium with a glassy phase having a free energy of formation of (73 600 — 36.8T)J from 0.5 CaO + 0.5 MgO. The apparent Arrhenius parameters for the decomposition are calculated as E = 194 kJ mole-1 and activation entropy = 93 JK-1 (mole C02)-1. 

RATE COEFFICIENTS AND ARRHENIUS PARAMETERS FOR NITRATION OF HETEROCYCLICS IN NITRIC ACID-SULPHURIC ACID50... 

Arrhenius parameters for nitration of 4-aikylphenyltrimethyiammonium ions in nitric acid-sulphuric acid mixtures (Table 12). It was argued that the observed Baker-Nathan order of alkyl substituent effect was, in fact, the result of a steric effect superimposed upon an inductive order. However, a number of assumptions were involved in this deduction, and these render the conclusion less reliable than one would like it would be useful to have the thermodynamic parameters for nitration of the methyl substituted compound in particular, in order to compare with the data for the /-butyl compound, though experimental difficulties may preclude this. It would not be surprising if a true Baker-Nathan order were observed because it is observed for all other electrophilic substitutions in this medium1. 

RELATIVE RATES AND ARRHENIUS PARAMETERS FOR REACTION OF XC6H4NMe+ AND... 

Mason256 has measured the second-order rate coefficients and Arrhenius parameters for the chlorination of benzene, biphenyl, naphthalene, and phe-nanthrene in acetic acid (containing 0.05 % water) and these are given in Table 62. 

SECOND-ORDER RATE COEFFICIENTS (10" A 2) AND ARRHENIUS PARAMETERS FOR REACTION of ArH with Cl2 in HOAc236... 

The two constants, A and Ea, are known as the Arrhenius parameters for the reaction and are found from experiment A is called the pre-exponential factor, and , is the activation energy. Both A and a are nearly independent of temperature bur have values that depend on the reaction being studied. 

Only fragmented data are available on polymerization of other methacrylates. Propagation constants and the respective Arrhenius parameters for the homopolymerization of various methacrylates initiated by sodium metallo-organics were reported recently +3,56) and are given in Table 2. 

KINETIC ISOTOPE EFFECTS AND ARRHENIUS PARAMETERS FOR THE OXIDATION OF FLUORAL HYDRATE BY Mn(VH) AND Mn(VI)... 

The ten-fold reduction in rate on deuteration without changing the stoichiometry provides strong evidence that both sets of products originate in a common step. The Arrhenius parameters for this reaction, E = 13.3 kcal.mole A5 = —17 eu) invite comparison with those for the oxidation of free formate ion E = 12.4 kcal.mole S AS = —15 eu). 

The stoichiometry of the reduction by Fe(ll) of cumene hydroperoxide is 1 1 (in contrast to reduction of H2O2) but the ratio A[Fe(II)]/A[ROOH] increases greatly in the presence of oxygen. The Arrhenius parameters for reduction of this and related hydroperoxides are quite similar to those of the Fenton reaction (Table 21). The production of acetophenone and ethane in high yield and the simple, second-order kinetics are consistent with the scheme... 

The ability of the stable free radical diphenylpicrylhydrazyl (DPPH) to act as an efficient trap for reactive radicals such as 804 and OH- has been utilised by Bawn and Margerison in their examination of the Ag -S20g couple. The disappearance of the intensely coloured DPPH gave excellent zero-order kinetics the rate as a whole was identical with that found by Fronaeus and Ostman and 2 was given by 3.1 x 10 exp(—17.9x lO /RT) l.mole sec A Sengar and Gupta have also determined Arrhenius parameters for this reduction and have compared them with those for some redox processes (Table 23). 

This type of reaction is involved as an intermediate step in few synthetically useful reactions, in the formation of polysulfones by copolymerization of an olefin with SO 2, as well as in aerosol formation in polluted atmospheres. We will discuss later in some detail the most important chain reactions involving step 11. However, Good and Thynne determined the Arrhenius parameters for the addition of methyl and ethyl radicals to SO2 in gas phase, the rate constants being 5 x 10 and 4 x 10 s respectively at ambient... 

Table 11. Arrhenius parameters for the spin-state transition in rFet2-nicl.irPF 1. at nr siirpe ...

In this chapter, we describe how experimental rate data, obtained as described in Chapter 3, can be developed into a quantitative rate law for a simple, single-phase system. We first recapitulate the form of the rate law, and, as in Chapter 3, we consider only the effects of concentration and temperature we assume that these effects are separable into reaction order and Arrhenius parameters. We point out the choice of units for concentration in gas-phase reactions and some consequences of this choice for the Arrhenius parameters. We then proceed, mainly by examples, to illustrate various reaction orders and compare the consequences of the use of different types of reactors. Finally, we illustrate the determination of Arrhenius parameters for die effect of temperature on rate. 

These results are similar to those in the previous section, with n — 1 replacing n, and similar conclusions about temperature dependence can be drawn, except that for a first-order reaction, ea = eAp and A = A,. The relationships of these differing Arrhenius parameters for a third-order reaction are explored in problem 4-12. 

Determine the Arrhenius parameters for the reaction C2H4 + C4H6 - C6H10 from the following data (Rowley and Steiner, 1951) ... 

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