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Unformatted text preview: Kinetic Theory of Gases: Elementary Ideas 9th February 2011 1 Kinetic Theory: A Discussion Based on a Sim plified View of the Motion of Gases 1.1 Pressure: Consul Engel and Reid (Ch. 33.1) for a discussion of the derivation for the pressure of a rarefied collection of particles of mass m . In the following, we provide a connection from the onedimensional version to the full scalar pressure. The connection is not quite direct from the discussion of Engel and Reid. In 3D, for a collection of many particles (on the order of Avogadro num ber), using average values of velocity and velocity components (in Carte sian coordinates); these are not generalized coordinates (as physicists would consider), the total kinetic energy is: KE total = N 2 m ( ~v ~v ) = N 2 m ( v 2 x + v 2 y + v 2 z ) = N 2 m v 2 x + N 2 m v 2 y + N 2 m v 2 z = ( KE ) x + ( KE ) y + ( KE ) z The last equality is really just a notational trick; there really does not exist a thermodynamic or kinetic property ( KE ) x or ( KE ) y or ( KE ) z ! The lowercase m is mass. The velocity is a vector so the v 2 we treat casually is really a dot product . The pressure components for the x , y , and z directions as we determined in class are: 1 p x = N V m v 2 x = 1 V 2 ( KE ) x p y = N V m v 2 y = 1 V 2 ( KE ) y p z = N V m v 2 z = 1 V 2 ( KE ) z N is the number of particles. V is the volume of space we are considering. From statistical mechanics (which you will learn more about in the future) we have the relation for the special case of a fluid or state of matter with extremely weak interactions (or no interactions): ( KE ) x = N 2 N Avogadro RT ( KE ) y = N 2 N Avogadro RT ( KE ) z = N 2 N Avogadro RT Thus, 2 ( KE ) x = N N Avogadro RT 2 ( KE ) y = N N Avogadro RT 2 ( KE ) z = N N Avogadro RT Substituting the above relations for 2 ( KE x ), etc. into the pressure equations yields: p x = N V 1 N Avogadro RT p y = N V 1 N Avogadro RT p z = N V 1 N Avogadro RT Recall that N N Avogadro is the number of moles N moles . Thus, the equations for pressure become: 2 p x = N moles V RT p y = N moles V RT p z = N moles V RT Here, we stop and realize that we have a xcomponent of pressure, a y component and a zcomponent. This is not an artificial result, as rigorously, pressure is a tensorial property (it is a 3x3 matrix). The diagonal elements (which we have computed) have special meaning in that they can be used to determine the pressure as we know it. Rigorously, the scalar pressure (that we normally measure and talk about) is determined from the trace of the pressure tensor (or matrix). This is: p scalar total = 1 3 ( p x + p y + p z ) = 1 3 N moles V ( RT + RT + RT ) = N moles V R T pressure = N moles V R T This should be a more convincing argument for the equality of kinetic theory description of fluids to that of an ideal gas....
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This note was uploaded on 02/02/2012 for the course CHEM 444 taught by Professor Dybowski,c during the Fall '08 term at University of Delaware.
 Fall '08
 Dybowski,C
 Physical chemistry, pH

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