Perrin kinetics

This kinetic explanation of osmotic pressure has recently received experimental support in the beautiful researches of Perrin on the Brownian movement (Urcwnian Movement and Molecular lteality, J. Perrin, trails. F. Soddy, 1910). 

The observation of second-order kinetics (ku) for the spectral decay of the anisole cation radical in Fig. 15 points to the disappearance of AN + - after its separation from the initially formed triad in (63). Owing to the high yields of nitroanisoles obtained, such a process can be formulated as in Scheme 11 as the bimolecular (homolytic) reaction in (64) that produces the critical Wheland intermediate in aromatic nitration according to Perrin (1977) and Ridd (1991). 

Perhaps best known of Perrin s work is his spirited defense of kinetic theory and physical atomism entitled Les atomes (1913), in which he made use of his own work on Brownian motion, in combination with studies of cathode rays and x-rays, ionization, radioactivity, radiation, and quantum theory.72 About the time of the 1911 Solvay physics conference, Perrin shifted from Brownian motion to work on thin films, fluorescence, and photochemistry, partly to test the early quantum theory and especially to study individual atom-based fluctuations. 

Among French physical chemists, Perrin and his immediate circle of colleagues were unique in interesting themselves in kinetics and activation mechanisms. The other best-known practitioners of physical chemistry in France, Henry LeChatelier and Pierre Duhem, concentrated on studies of chemical equilibria and thermodynamic potential. 

Like so many physical chemists and physicists interested in kinetics, one of Perrin s starting points was Arrhenius s activity formula (1889) for the probability of transformation of a molecule at temperature T, where the probability is... 

Letter from Perrin to Einstein, 28 August 1919 Einstein to Perrin, 5 November 1919, Einstein Collection, Institute for Advanced Study, Princeton (now housed in Jerusalem), cited originally in Nye, Molecular Reality, n. 93, 177. See F. A. Lindemann, "Note on the Significance of the Chemical Constant and Its Relation to the Behaviour of Gases at Low Temperatures," Phil.Mag. 39 (1920) 2125, cited in M. Christine King and Keith T. Laidler, "Chemical Kinetics and the Radiation Hypothesis," Archive for History of Exact Sciences 30 (1984) ... 

A good deal of this work had no impact in the development of models of molecular structure and the elucidation of reaction mechanisms one reason was Perrin s own coolness to quantum wave mechanics. 108 Another, according to Oxford s Harold Thompson, who studied with Nernst and Fritz Haber, was that researchers like Lecomte "did not know enough chemistry he was a physicist." 109 Perrin, too, approached physical chemistry as a physicist, not as a chemist. He had little real interest or knowledge of organic chemistry. But what made his radiation hypothesis attractive to many chemists was his concern with transition states and the search for a scheme of pathways defining chemical kinetics. 

We have seen, for example, that members of Lespieau s school of theoretical chemistry narrated a history of battle within the field of French chemistry against the institutionally powerful intellectual disciples of Deville, Berthelot and Jungfleisch, on the one hand, and against the conceptually powerful, if institutionally weak, school of Duhem, on the other hand. They situated themselves adjacent and sometimes interior to the scientific circle of Perrin, with its focus on kinetics and the radiation hypothesis, and in opposition to the... 

The only apparently viable alternative mechanism to explain the observed unimolecular behavior is one that was originally proposed in 1919 by Perrin and became known as the radiation hypothesis. In the absence of any significant body of kinetic data, Perrin proposed that reactant molecules obtain the energy required... 

The Perrin-like expression in equation 27 was used to fit the kinetic decay trace of polymer 7 the fit is illustrated in Figure 5. 

M. Shiratani, J. Jolly, H. Videlot, J. Perrin Surface reaction kinetics of CH3 in CH4 rf discharge studied by time-resolved threshold ionization mass spectrometry. Jpn. J. Appl. Phys. 36, 4752 (1997)... 

The formation of NO2F (nitryl fluoride) from NO2 and F2 has been investigated by Perrine and Johnston over the temperature range 27.7-70.2 °C. Absorption spectroscopy at 4360 A was used to monitor the NO2 concentration as a function of time providing a means of extracting kinetic data. 

The kinetics of hydration and dehydration for quinazoline and 2-methyl-quinazoline were studied in great detail by Bunting and Perrin, and the pH-rate profiles between pH 0.5 and 12.0 were determined. The profiles for quinazoline are illustrated in Fig. 1. The rate of hydration was given by the expression in Eq. (2). 

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