Thermodynamics Maxwell-Boltzmann distribution

To understand how collision theory has been derived, we need to know the velocity distribution of molecules at a given temperature, as it is given by the Maxwell-Boltzmann distribution. To use transition state theory we need the partition functions that follow from the Boltzmann distribution. Hence, we must devote a section of this chapter to statistical thermodynamics. 

In summary, Eq. (86) is a general expression for the number of particles in a given quantum state. If t = 1, this result is appropriate to Fenni-rDirac statistics, or to Bose-Einstein statistics, respectively. However, if i is equated torero, the result corresponds to the Maxwell -Boltzmann distribution. In many cases the last is a good approximation to quantum systems, which is furthermore, a correct description of classical ones - those in which the energy levels fotm a continuum. From these results the partition functions can be calculated, leading to expressions for the various thermodynamic functions for a given system. In many cases these values, as obtained from spectroscopic observations, are more accurate than those obtained by direct thermodynamic measurements. 

The thermodynamic temperature is the sole variable required to define the Maxwell-Boltzmann distribution raising the temperature increases the spread of energies. 

At this point, it is worthwhile to return on the theoretical basis of the kinetic method, and make some considerations on the assumptions made, in order to better investigate the validity of the information provided by the method. In particular some words have to been spent on the effective temperamre The use of effective parameters is common in chemistry. This usually implies that one wishes to use the form of an established equation under conditions when it is not strictly valid. The effective parameter is always an empirical value, closely related to and defined by the equation one wishes to approximate. Clearly, is not a thermodynamic quantity reflecting a Maxwell-Boltzmann distribution of energies. Rather, represents only a small fraction of the complexes generated that happen to dissociate during the instrumental time window (which can vary from apparatus to apparatus). 

Although Boltzmann did not fully succeed in proving the tendency of the world to go to a final equilibrium state, there remain after all criticisms the following valuable results first, the derivation of the Maxwell-Boltzmann distribution for equilibrium states, then the kinetic interpretation of the entropy by the //-function, and finally the explanation of the existence of an integrating factor for dU+dA. In thermodynamics the existence of such a factor is always based on an unexplained hypothesis. 

Boltzmann connected his ideas with those of Rudolf Clausius, who had introduced the concept of entropy in 1865. Somehow related to heat, entropy was known to increase during irreversible processes, but its exact nature was unknown. From the distribution of gas atoms, Boltzmann described a quantity—later symbolized by the letter H—which is a minimum when atoms assume a Maxwell-Boltzmann distribution. He recognized his H function as the negative of entropy, which is a maximum when the atoms reach thermal equilibrium. Thus Boltzmann offered a kinetic explanation for entropy and, more generally, a connection between the behavior of atoms and thermodynamics. 

When H has reached its minimum value this is the well known Maxwell-Boltzmann distribution for a gas in thermal equilibrium with a uniform motion u. So, argues Boltzmann, solutions of his equation for an isolated system approach an equilibrium state, just as real gases seem to do. Up to a negative factor -k, in fact), differences in H are the same as differences in the thermodynamic entropy between initial and final equilibrium states. Boltzmann thought that his //-theorem gave a foundation of the increase in entropy as a result of the collision integral, whose derivation was based on the Stosszahlansatz. 

Ludwig Boltzmann (1844-1906), the Austrian physicist, is famous for his outstanding contributions to heat transfer, thermodynamics, statistical mechanics, and kinetic theory of gases. Boltzmann was a student of Josef Stefan and received his doctoral degree in 1866 under his supervision. The Stefan-Boltzmann law (1884) for black body radiation is the result of the associated work of Josef Stefan and Boltzmann in the field of heat transfer. Boltzmann s most significant works were in kinetic theory of gases in the form of Maxwell-Boltzmann distribution and Maxwell-Boltzmann statistics in classical statistical mechanics. 

A fluid composed of a single species is described by five fields the three components of the velocity, the mass density, and the temperature. This is a drastic reduction of the full description in terms of all the degrees of freedom of the particles. This reduction is possible by assuming the local thermodynamic equilibrium according to which the particles of each fluid element have a Maxwell-Boltzmann velocity distribution with local temperature, velocity, and density. This local equilibrium is reached on time scales longer than the intercollisional time. On shorter time scales, the degrees of freedom other than the five fields manifest themselves and the reduction is no longer possible. 

Maxwell-Boltzmann particles are distinguishable, and a partition function, or distribution, of these particles can be derived from classical considerations. Real systems exist in which individual particles are indistinguishable. For example, individual electrons in a solid metal do not maintain positional proximity to specific atoms. These electrons obey Fermi-Dirac statistics (133). In contrast, the quantum effects observed for most normal gases can be correlated with Bose-Einstein statistics (117). The approach to statistical thermodynamics described thus far is referred to as wave mechanics. An equivalent quantum theory is referred to as matrix mechanics (134—136). 

CTE is not realized in laboratory plasmas wich are optically thin (Planck s law is not valid). But the mass action law, the Boltzmann distribution and Maxwell distribution may be obeyed by a unique local temperature such that T, = T e = T = T, then one introduces the (complete) local thermodynamic equilibrium (LTE). Boltzmann and Saha s law are often obeyed only for highly excited levels, the plasma is then said to be in Local Partial Thermodynamic Equilibrium (LPTE). 

In practice, EPR samples consist of collections of many paramagnetic species, and not single isolated paramagnetic centers. If the population of radicals is in thermodynamic equilibrium, its statistical distribution is described by the Maxwell-Boltzmann equation... 

The zeroth moment of a distribution is 1, the first moment is < i>, the second moment is < P>, etc. The higher moments of a distribution hence compute successively higher averages of the distributions of the independent variable for example, in classical statistical thermodynamics the mean square velocity is the second moment of the Maxwell-Boltzmann speed distribution for an ideal gas, and is directly related to average kinetic energy < KE > = m < v >/2, and hence to temperature [= 3k TI2 for a monatomic gas]. 

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