Arguments for

If we wish to know the number of (VpV)-collisions that actually take place in this small time interval, we need to know exactly where each particle is located and then follow the motion of all the particles from time tto time t+ bt. In fact, this is what is done in computer simulated molecular dynamics. We wish to avoid this exact specification of the particle trajectories, and instead carry out a plausible argument for the computation of r To do this, Boltzmann made the following assumption, called the Stosszahlansatz, which we encountered already in the calculation of the mean free path ... 

The argument for the S 2 process, when the transition from acetic acid as solvent to nitric acid as solvent is considered, is less direct, for because of the experimental need to use less reactive compounds, zeroth-order nitration has not been observed in nitric acid. It can be estimated, however, that a substance such as nitrobenzene would react about 10 faster in first-order nitration in nitric acid than in a solution of nitric acid (7 mol 1 ) in acetic acid. Such a large increase is understandable in terms of the S z mechanism, but not otherwise. 

From the ratio of activities and measured values of n, the average number of initiator fragments per polymer can be determined. Carry out a similar argument for the ratio of activities for polystyrene and evaluate the average number of initiator fragments per molecule for each polymer from the following datat ... 

Iq = zero-order Bessel function of an imaginary argument. For large u, 7 (t/) -e /V2. Hence for large n,... 

Greenfield, P. 1996 Cogent Argument for Better Design Skills. Professional Engineering, January, 13-14. 

In the United States, regulation of emissions from new automotive vehicles has followed the prototype-replicate route. The argument for routine annual automobile inspection is that cars should be regularly inspected for safety (brakes, lights, steering, and tires) and that the additional time and cost required to check the car s emission control system during the same inspection will be minimal. Such an inspection certainly pinpoints cars whose emission control system has been removed, altered, damaged, or deteriorated and force such defects to be remedied. The question is whether... 

Chapter 6 makes a strong argument for pollution prevention (P2) practices, but is prudent in pointing out that there are many situations where conventional pollution... 

It is worth noting that there is no need to optimize over ei- As previously shown, when 2 was set equal to its lowest permissible value (0.(X)1), S was selected as the optimal process MSA above the pinch. On the pinch diagram, as increases, S2 moves to the right, and the same arguments for selecting Si over S2 remain valid. 

Fluorinated cyclobutanes and cyclobutenes are relatively easy to prepare because of the propensity of many gem-difluoroolefins to thermally cyclodimerize and cycloadd to alkenes and alkynes. Even with dienes, fluoroolefins commonly prefer to form cyclobutane rather than six-membered-ring Diels-Alder adducts. Tetrafluoroethylene, chlorotrifluoroethylene, and l,l-dichloro-2,2-difluoroethyl-ene are especially reactive in this context. Most evidence favors a stepwise diradical or, less often, a dipolar mechanism for [2+2] cycloadditions of fluoroalkenes [S5, (5], although arguments for a symmetry-allowed, concerted [2j-t-2J process persist [87], The scope, characteristic features, and mechanistic studies of fluoroolefin... 

Now suppose that, from this equilibrium situation, the final state is instantaneously removed. The production of transition state species by the product state will cease. However, the production of transition state species by the reactant state is unaffected by this suppression of the final state, and, according to the third postulate of the theory, the rate of reaction is a function of the transition state concentration formed from the reactant state. This is the usual argument for the equilibrium assumption. Despite its apparent artificiality, the equilibrium assumption is generally considered to be fairly sound, with the possible exception of its application to very fast reactions. ... 

For this type of reaction the value of the solvent deuterium isotope effect is often a conclusive argument for the proposed mechanism 16). Rate measurements of 1 in acetic acid-acetate buffers in light and heavy water resulted in an isotope effect ktiiO lkozo of 2.5, and A oac/ doac of 9. A ratedetermining proton transfer to the /3-carbon atom of the enamine has been proposed and accounts for the experimental results I6-18 Eq. (5). 

FMO theory was developed at a time when detailed calculations of reaction paths were infeasible. As many sophisticated computational models, and methods for actually locating the TS, have become widespread, the use of FMO arguments for predicting reactivity has declined. The primary goal of computational chemistry, however, is not tc... 

---