A large number of data points for the vibrational relaxation time (pτv in atm sec) of simple systems have been logarithmically plotted vs (T°K)—⅓. It appears that each system is well represented by a straight line, and that most of these straight lines when extended to higher temperatures intersect near the point [pτv=10—8 atm sec, (T°K)—⅓=0.03]. Systems with a small reduced mass μ are exceptions to such a simple convergence, and in an improved scheme, the location of the convergence point is dependent on the reduced mass. Such a presentation has lead to an empirical equation correlating available measurements of vibrational relaxation times: log10(pτv)=(5.0×10−4)μ12θ43[T−13−0.015μ14]−8.00, where θ is the characteristic temperature of the oscillator in K deg. This equation reproduces the measured times within 50% for systems as diverse as N2, I2, and O2–H2. In the worst case thus far, O2–Ar near 1000°K, it is off by a factor of 5.

Systematics of Vibrational Relaxation

This is a study of the thermodynamics of nonlinear materials with internal state variables whose temporal evolution is governed by ordinary differential equations. After employing a method developed by Coleman and Noll to find the general restrictions which the Clausius—Duhem inequality places on response functions, we analyze various types of dynamical stability that can be exhibited by solutions of the internal evolution equations. We also discuss integral dissipation inequalities, conditions under which temperatures can be associated with internal states, and the forms taken by response functions when the material is a fluid.

Thermodynamics with Internal State Variables

Recent attempts have been made to assess the relative merits of the free volume and entropy theories of viscous flow in glass‐forming liquids by accurate measurement of viscosity over wide temperature ranges, and subsequent comparison with the equations derived from these theories. In the author's view, this effort is misguided. The theories are crude and qualitative, and such tests are too stringent. It is better to make qualitative or semiquantitative comparison of a wide variety of physical phenomena; judged by this criterion, the entropy theory appears more successful. It is conjectured that further progress can be made by accepting the crude, naive character of any model we are likely to find tractable for the foreseeable future, and recognizing both the values and limitations of such models. A picture of the flow process in viscous liquids is proposed, in an attempt to answer certain questions about the molecular steps in flow either answered unsuccessfully or ignored by present theories, in the hop...

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Viscous Liquids and the Glass Transition: A Potential Energy Barrier Picture

In this article we shall present a summary of the various stochastic approaches and applications to chemical reaction kinetics, but before discussing these we first briefly introduce the basic ideas and definitions of classical or deterministic chemical kinetics. One of the basic questions to which chemists address themselves is the rate of chemical reactions, or in other words, how long it takes for a chemical reaction to attain completion, or equilibrium. Apparently the first significant quantitative investigation was made in 1850 by L. Wilhelmy [93]. He studied the inversion of sucrose (cane sugar) in aqueous solutions of acids, whose reaction is He found empirically that the rate of decrease of concentration of sucrose was simply proportional to the concentration remaining unconverted, i.e., if S(t) is the concentration of sucrose, then The constant of proportionality is called the rate constant of the reaction. If S o is the initial concentration of sucrose, then Since then an enormous number of reactions has been studied and the field of chemical kinetics is now one of the largest areas of chemical research. The importance of the field lies in the fact that it yields concise expressions for the time dependence of reactions, predicts yields, optimum economic conditions, and gives one much insight into the actual molecular processes involved. The detailed molecular picture of a reaction process is called the mechanism of the reaction.

Theodore A. Litovitz

Papers

Absorption and Dispersion of Ultrasonic Waves

Absorption and Dispersion of Ultrasonic Waves