Translation kinetics

F2. Frank-Kamentskii, D. A., Diffusion and Heat Exchange in Chemical Kinetics (translation). Princeton Univ. Press, Princeton, New Jersey, 1955. 

D. A. Frank-Kamenetsky, Diffusion and Heat Transfer, in Chemical Kinetics (Translated from Russian), Princeton, Princeton University Press, 1955. 

Pannetier, G., and Souchay, P., Chemical Kinetics, translated by H. D. Gesser and H. H. Emond, pp. 177— 178, Elsevier, Amsterdam, 1967. Adapted with permission. 

The energy of molecules consists of kinetic (translational), rotational, vibrational, and electronic... 

Okazaki et al. found that the thermal decomposition of 5-phenylthiatriazole in the presence of alkenes gives no episulfides and suggested that this is explicable in terms of low excess kinetic (translational) energy of sulfur atoms generated in the thermal reaction.22... 

As we showed in Section 6.2, the stationary states for a particle in a box have specific values for kinetic (translational) energy. For a one-dimensional box, we showed that En = n2h2/%mL2. For a three-dimensional box (side length L, volume V = l ) each of the three degrees of freedom (motion in the x-, y-, and z-directions) has its own quantum number, usually called nx,ny, and nz respectively. The energy is given by... 

Kipin, J. 961) Physical Fundamentals of Nuclear Reactor Kinetics. Translation from English, Atomizdat, Moscow (in Russian). 

Slow kinetics translates to additional time required for the extraction and/or release step. Sixth, and last, there can be no partitioning of the complexing agent into the feed or receiving phases. This effect would continuously decrease the amount of complexing agent available as the separation process is cycled. 

This chapter gives only a glimpse of a vast field surveyed by D. A. Frank-Kame-netskii in Dijffusion and Heat Exchange in Chemicrd Kinetics, translated by N. Thon, Princeton University Press, Princeton, N.J., 1955. This book, though somewhat out of date, b still an excellent introduction to the subject. It contains valuable details on the topics summarized in Sections 2, 3 and 4 of this qhapter. 

Thus far very little has been said about how intact ionized molecules, e.g. those formed by soft ionization techniques like the API methods (Sections 5.3.3-5.3.6), can be induced to dissociate for subsequent MS/MS analysis. (In fact any ion produced in an ion source can be miz selected and subjected to MS/MS analysis). Soft ionization does not produce metastable ions (see above) in any abundance if at aU. Historically the most common method of ion activation has heen coUisional activation (CA), wherehy ions are accelerated through a defined potential drop to transform their electrical potential energy into kinetic (translational) energy, and are then caused to collide with gas molecules that are dehherately introduced into the ion trajectory the history of this approach has heen described in an excellent overview (Cooks 1995). This involves conversion of part of the ions kinetic energy into internal energy that in turn leads to fragmentation. It is still by far the most commonly used method. 

The atoms of the adsorbate and adsorbent are not without internal motion both vibrate about their bonds. The higher the temperature of the adsorption system the higher is the amplitude/frequency of these vibrations, in addition to their kinetic translation motion. Thus, an adsorbed molecule does not remain stationary at an adsorption site. It may move to another adsorption site or it may return to the adsorptive. Within the system, thermal spikes, or sites of higher than average amplitude, move throughout the surface, and these have sufficient energy (equivalent to a rise in temperature) to dislodge the molecule from a particular site. The adsorbate molecule is ejected and as the thermal spike is transitory it is replaced by another adsorbate molecule such that at all times the measured extents of adsorption remain constant. 

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