Ideal gas theory

So these coincide with the non relativistic result. Indeed, for a non-relativistic ideal gas theory - Maxwellian theory (for ID systems)- we obtain... 

This is the overriding assumption in ideal gas theory and perhaps the worst. Composition and temperature changes drastically in the nozzle for most high temperature systems however, the low temperature decomposition of monopropellants can be treated as ideal. 

Of course, no gas is really ideal. The ideal gas theory ignores certain facts about real gases. For example, an ideal gas particle does not take up any space. In fact, you know that all particles of matter must take up space. Gas particles are small and far apart, however. Thus the space occupied by the particles is insignificant compared to the total volume of the container. You will learn more about the behaviour of real gases in Chapter 12. 

Since the reform reaction is not tabulated in the JANAF tables, ideal gas theory, an approximation, is the only alternative. 

Finally, ideal gas theory required the inclusion of time. Molecules move randomly and if there are enough of them in enough space, the gas would look uniform. This time dimension we call t. 

In summary, we can say that ideal gas theory required only N, 3D, and t, molecular units, space within which to move, and time to permit movement. The Van der Waals equation added 3d and A, while the one-way behavior encountered in mixing added V7. 

These six dimensions are here focused on and they rather naturally divide into three pairs, two involving time, two involving space, and two recognizing the conti-nuity/discontinuity dichotomy. For ease in visualization, the pairs can be presented as opposite faces of a cube (Figure 1) on which ideal gas theory requires only half the faces, one face from each pair, the three meeting at one vertex of the cube. 

Ideal gas theory treats the molecules as rigid spheres having radii and tb. They... 

The similitude between it A diagrams and PVT diagrams was exploited in the development of equations of state for the films deposited on the air-water interface (Gaines, 1966). Using an analogy with ideal gas theory, a simple model assumes that in the gas region, molecules at the air-water interface have a mobility dependent on their thermal kinetic energy... 

In addition to mean free path, the flux of atoms striking a surface, or the approximate time between collisions on a particular atomic site on a surface, is important. Ideal gas theory yields a relation between flux and pressure of... 

Another important accomplislnnent of the free electron model concerns tire heat capacity of a metal. At low temperatures, the heat capacity of a metal goes linearly with the temperature and vanishes at absolute zero. This behaviour is in contrast with classical statistical mechanics. According to classical theories, the equipartition theory predicts that a free particle should have a heat capacity of where is the Boltzmann constant. An ideal gas has a heat capacity consistent with tliis value. The electrical conductivity of a metal suggests that the conduction electrons behave like free particles and might also have a heat capacity of 3/fg,... 

Substances at high dilution, e.g. a gas at low pressure or a solute in dilute solution, show simple behaviour. The ideal-gas law and Henry s law for dilute solutions antedate the development of the fonualism of classical themiodynamics. Earlier sections in this article have shown how these experimental laws lead to simple dieniiodynamic equations, but these results are added to therniodynaniics they are not part of the fonualism. Simple molecular theories, even if they are not always recognized as statistical mechanics, e.g. the kinetic theory of gases , make the experimental results seem trivially obvious. 

The parameters a and b are characteristic of the substance, and represent corrections to the ideal gas law dne to the attractive (dispersion) interactions between the atoms and the volnme they occupy dne to their repulsive cores. We will discnss van der Waals equation in some detail as a typical example of a mean-field theory. 

It has long been known from statistical mechanical theory that a Bose-Einstein ideal gas, which at low temperatures would show condensation of molecules into die ground translational state (a condensation in momentum space rather than in position space), should show a third-order phase transition at the temperature at which this condensation starts. Nonnal helium ( He) is a Bose-Einstein substance, but is far from ideal at low temperatures, and the very real forces between molecules make the >L-transition to He II very different from that predicted for a Bose-Einstein gas. 

In the case of bunolecular gas-phase reactions, encounters are simply collisions between two molecules in the framework of the general collision theory of gas-phase reactions (section A3,4,5,2 ). For a random thennal distribution of positions and momenta in an ideal gas reaction, the probabilistic reasoning has an exact foundation. Flowever, as noted in the case of unimolecular reactions, in principle one must allow for deviations from this ideal behaviour and, thus, from the simple rate law, although in practice such deviations are rarely taken into account theoretically or established empirically. 

Turning finally to the Interpretation of Graham s experimental resul on transpiration, the theory of viscous flow of an ideal gas through a Ion capillary gives... 

The fugacity coefficient of thesolid solute dissolved in the fluid phase (0 ) has been obtained using cubic equations of state (52) and statistical mechanical perturbation theory (53). The enhancement factor, E, shown as the quantity ia brackets ia equation 2, is defined as the real solubiUty divided by the solubihty ia an ideal gas. The solubiUty ia an ideal gas is simply the vapor pressure of the sohd over the pressure. Enhancement factors of 10 are common for supercritical systems. Notable exceptions such as the squalane—carbon dioxide system may have enhancement factors greater than 10. Solubihty data can be reduced to a simple form by plotting the logarithm of the enhancement factor vs density, resulting ia a fairly linear relationship (52). 

The traditional unipolar diffusion charging model is based on the kinetic theory of gases i.e., ions are assumed to behave as an ideal gas, the properties of which can described by the kinetic gas theory. According to this theory, the particle-charging rate is a function of the square of the particle size dp, particle charge numbers and mean thermal velocity of tons c,. The relationship between particle charge and time according White s... 

Section 5.6 considers the kinetic theory of gases, the molecular model on which the ideal gas law is based. Finally, in Section 5.7 we describe the extent to which real gases deviate from the law. ... 

There is a reasonable explanation for this type of deviation. The kinetic theory, which explains the pressure-volume behavior, is based upon the assumption that the particles exert no force on each other. But real molecules do exert force on each other The condensation of every gas on cooling shows that there are always attractive forces. These forces are not very important when the molecules are far apart (that is, at low pressures) but they become noticeable at higher pressures. With this explanation, we see that the kinetic theory is based on an idealized gas—one for which the molecules exert no force on each other whatsoever. Every gas approaches such ideal behavior if the pressure is low enough. Then ihe molecules are, on the average, so far apart that then-attractive forces are negligible. A gas that behaves as though the molecules exert no force on each other is called an ideal gas or a perfect gas. 

The quantities n, V, and (3 /m) T are thus the first five (velocity) moments of the distribution function. In the above equation, k is the Boltzmann constant the definition of temperature relates the kinetic energy associated with the random motion of the particles to kT for each degree of freedom. If an equation of state is derived using this equilibrium distribution function, by determining the pressure in the gas (see Section 1.11), then this kinetic theory definition of the temperature is seen to be the absolute temperature that appears in the ideal gas law. 

We may therefore sum up the results in the statement that the laws of osmotic pressure of a dilute solution are formally identical with the laws of gas pressure of an ideal gas (van t Hoff s Gaseous Theory of Solution). 

It has been assumed in the deduction of (1) that the solute is an ideal gas, or at least a volatile substance. The extension of the result to solutions of substances like sugar, or metallic salts, must therefore be regarded as depending on the supposition that the distinction between volatile and non-volatile substances is one of degree rather than of kind, because a finite (possibly exceedingly small) vapour pressure may be attributed to every substance at any temperature above absolute zero. This assumption is justified by the known continuity of pleasure in measurable regions, and by the kinetic theory of gases. 

The energy system we choose to use in deriving an expression for / is the translational energy of the ideal gas. From kinetic-molecular theory we know that f/trans, the average translational energy is given by... 

In the previous section, the molecular basis for the processes of momentum transfer, heat transfer and mass transfer has been discussed. It has been shown that, in a fluid in which there is a momentum gradient, a temperature gradient or a concentration gradient, the consequential momentum, heat and mass transfer processes arise as a result of the random motion of the molecules. For an ideal gas, the kinetic theory of gases is applicable and the physical properties p,/p, k/Cpp and D, which determine the transfer rates, are all seen to be proportional to the product of a molecular velocity and the mean free path of the molecules. 

The formal thermodynamic analogy existing between an ideal rubber and an ideal gas carries over to the statistical derivation of the force of retraction of stretched rubber, which we undertake in this section. This derivation parallels so closely the statistical-thermodynamic deduction of the pressure of a perfect gas that it seems worth while to set forth the latter briefly here for the purpose of illustrating clearly the subsequent derivation of the basic relations of rubber elasticity theory. 

A theory close to modem concepts was developed by a Swede, Svante Arrhenins. The hrst version of the theory was outlined in his doctoral dissertation of 1883, the hnal version in a classical paper published at the end of 1887. This theory took up van t Hoff s suggeshons, published some years earlier, that ideal gas laws could be used for the osmotic pressure in soluhons. It had been fonnd that anomalously high values of osmotic pressure which cannot be ascribed to nonideality sometimes occur even in highly dilute solutions. To explain the anomaly, van t Hoff had introduced an empirical correchon factor i larger than nnity, called the isotonic coefficient or van t Hoff factor,... 

An expression for the absolute rate of condensation can be developed readily if the simple kinetic theory of gases and the ideal gas law are applied (S2) ... 

A quantity of central importance in the study of uniform liquids is the pair correlation function, g r), which is the probability (relative to an ideal gas) of finding a particle at position r given that there is a particle at the origin. All other structural and thermodynamic properties can be obtained from a knowledge of g r). The calculation of g r) for various fluids is one of the long-standing problems in liquid state theory, and several accurate approaches exist. These theories can also be used to obtain the density profile of a fluid at a surface. 

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