Mechanical experimental evidences

Experimental evidence such as toxicity tests or the induction of disease under controlled conditions (Item 6) can also be coupled with field observations to establish cause-effect mechanisms. Experimental evidence is critical for testing specific predictions made by hypotheses designed to predict large-scale relationships and should be included whenever practical. 

If it can be shown that yy is equal to k, this is a reasonable reaction mechanism (experimental evidence does support this assumption). 

Oxy radicals add to olefins by both intermolecular and intramolecular mechanisms. Experimental evidence has indicated that intramolecular addition (Reaction H) may be much more important than its intermolecular counterpart (10, 11). 

With the general mechanism of olefin metathesis established by experimental work, early theoretical studies focused on the details of several of the steps outlined above. Ligand exchange to form the initial olefin complex could occur by either an associative or dissociative mechanism. Experimental evidence from Grubbs and coworkers [2] pointed to a dissociative process. The structure of the active olefin complex was also a matter of uncertainty, as both bottom-bound (trans to L) and side-bound (cis to L) complexes have been reported (Chapter 8). Finally, the detailed structure and reactivity of the metallacyclobutane have been the focus of several theoretical investigations, as this intermediate was not initially experimentally observed (Chapter 8). 

Numerous examples of polymer flow models based on generalized Newtonian behaviour are found in non-Newtonian fluid mechanics literature. Using experimental evidence the time-independent generalized Newtonian fluids are divided into three groups. These are Bingham plastics, pseudoplastic fluids and dilatant fluids. 

The mechanism includes two single electron transfers (steps 1 and 3) and two proton transfers (steps 2 and 4) Experimental evidence indicates that step 2 is rate determining and it is believed that the observed trans stereochemistry reflects the dis tribution of the two stereoisomeric alkenyl radical intermediates formed in this step... 

Physical or chemical vapor-phase mechanisms may be reasonably hypothesized in cases where a phosphoms flame retardant is found to be effective in a noncharring polymer, and especially where the flame retardant or phosphoms-containing breakdown products are capable of being vaporized at the temperature of the pyrolyzing surface. In the engineering of thermoplastic Noryl (General Electric), which consists of a blend of a charrable poly(phenylene oxide) and a poorly charrable polystyrene, experimental evidence indicates that effective flame retardants such as triphenyl phosphate act in the vapor phase to suppress the flammabiUty of the polystyrene pyrolysis products (36). 

Germicidal Properties. The germicidal activity of aqueous chlorine is attributed primarily to HOCl. Although the detailed mechanism by which HOCl kills bacteria and other microorganisms has not been estabUshed, sufficient experimental evidence has been obtained to suggest strongly that the mode of action involves penetration of the cell wall followed by reaction with the enzymatic system. The efficiency of destmction is affected by temperature, time of contact, pH, and type and concentration of organisms (177). 

The mechanism by which TBT causes these effects has been extensively stiidied. The androgenic effects of TBT appear to be caused by interference with steroid biosynthesis rather than by mimicking the action of testosterone at the androgen receptor. Exposure of female molluscs to TBT leads to an elevation in testosterone in the haemolymph. " Much of the experimental evidence... 

Concept of quantum-mechanical tunnelling in proton-uansfer reactions introduced (without experimental evidence) by several authors. 

The latter mechanism is characterized by a transition-state structure of type 64 and by its being (in part) analogous to the mechanism at a saturated carbon. The preference of a two-step mechanism to the apparently simpler one-step mechanism is suggested by the isolation of Meisenheimer complexes and by the kinetics of their formation. The experimental evidence on these... 

The attack on the aromatic nucleus by hydroxyl radicals is probably analogous to that by phenyl and methyl radicals, Eq. (34a,b). Evidence that the first step is the addition of hydroxyl radical to benzene, rather than abstraction of a hydrogen atom, has recently been adduced from a study of the radiolysis of water-benzene mixtures. The familiar addition complex may undergo two reactions to form the phenolic and dimeric products respectively, Eq. (34a,b). Alternative mechanisms for the formation of the dimer have been formulated, but in view of the lack of experimental evidence for any of the mechanisms further discussion of this problem is not justified. 

The mechanism of the decarboxylation of isoxazole-3-car boxy lie acids has not yet been specially studied, but the available experimental evidence allows some suggestions to be made. It seems that on heating isoxazole carboxylic acids in solution, or in the presence of arylhydrazines, it is the acid anion (158) formed which is being de-... 

The stereospecificity of the methylene transfer provides compelling support for a concerted mechanism and this conclusion has rarely been disputed. It is instructive, however, to review the experimental evidence that allowed for the elimination of the alternative mechanistic proposals, namely, a radical addition and a carbome-tallation (Scheme 3.4). 

In conclusion, it may be said that a lot of literature has been published that favors the Frye and Horst mechanism of stabilization. Most of this is based on studies done on low-molecular weight model compound for al-lylicchlorines in PVC, i.e., 4-chloro-2-hexene. Although the large contribution of these studies toward understanding the mechanism of stabilization of PVC cannot be denied, the extrapolation of these results to the processes involved in the actual stabilization of the polymer should be done with extreme care. The polymer represents a complex mixture of macromolecules, which in the melt is not only physically a very different system compared to the low-molecular weight model compound, but invariably contains, apart from stabilizers, other additives, such as plasticizers, lubricants, processing aids, etc., that further complicate the situation. The criticism of the Frye and Horst mechanism is also based on solid experimental evidence, and hence, the controversy is still very much alive. 

The following evidence has been obtained (1) The reaction occurs much faster in DMF than in ethanol. (2) The corresponding ethyl ester (RCO2CH2CH3) cleaves approximately 10 times more slowly than the methyl ester. Propose a mechanism for the reaction. What other kinds of experimental evidence could you gather to support your hypothesis ... 

It is important to point out one of the limitations of mechanism studies. Usually more than one mechanism is compatible with the same experimentally obtained rate expression. To make a choice between alternative mechanisms, other evidence must be considered. A classic example of this situation is the reaction between hydrogen and iodine... 

There is experimental evidence to suggest that anion and cation diffusion can have different mechanisms [70]. The temperature variation of the diffusion coefficients of 1,1 P and 7 Li in aPEO-LiPF6 shows quite different trends. The 31P diffusion coefficients follow a VTF-type de-... 

Of course in solution such an intermediate, if formed at all, would be very shortlived and could be the species responsible for the side reaction which produces some oligomerization of the furan ring. However, any interpretation of the mechanism of oligomerization must be regarded at this point as highly speculative since there is an obvious need for more experimental evidence, particularly concerning the structure of the products. 

In all these investigations Lewis acids were used as initiators at temperatures between -30 and 60 °C. The arguments used to substantiate the validity of structure 12 are unconvincing to this reviewer particularly because of the lack of sufficient experimental evidence. A subsequent paper on this subject40 did not improve the understanding of either the polymer structure or the mechanism. 

Stoicescu and Dimonie103 studied the polymerization of 2-vinylfuran with iodine in methylene chloride between 20 and 50 °C. The time-conversion curves were not analysed for internal orders but external orders with respect to catalyst and monomer were both unity. Together with an overall activation energy of 2.5 kcal/mole for the polymerization process, these were the only data obtained. Observations about the low DP s of the products, their dark colour, their lack of bound iodine and the presence of furan rings in the oligomers, inferred by infrared spectra (not reported), completed the experimental evidence. The authors proposed a linear, vinylic structure for the polymer, and a true cationic mechanism for its formation and discussed the occurrence of an initial charge-transfer complex on the... 

Dall Asta and Motroni (44, 57) provided direct experimental evidence for the transalkylidenation mechanism in the case of cycloalkenes. With a catalyst system consisting of WOCI4, C2H6A1C12, and benzoyl peroxide they prepared a random copolymer of cyclooctene and cyclopentene, the cyclo-pentene double bond being labeled with 14C. The distribution of the radioactivity in the copolymer formed will depend on the site of ring opening. 

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