Chapter 2: Q. 2.31 (page 79)
Fill in the algebraic steps to derive the Sackur-Tetrode equation
Short Answer
- The Sackur -Tetrode equation is
Chapter 2: Q. 2.31 (page 79)
Fill in the algebraic steps to derive the Sackur-Tetrode equation
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Get started for freeUse a computer to plot formula directly, as follows. Define =, so that =. Then, aside from an overall constant that we'll ignore, the multiplicity function is , where ranges from toand the factor of ensures that the height of the peak is equal to for any . Plot this function for=, and . Observe how the width of the peak decreases asincreases.
Use Stirling's approximation to find an approximate formula for the multiplicity of a two-state paramagnet. Simplify this formula in the limit to obtain . This result should look very similar to your answer to Problem ; explain why these two systems, in the limits considered, are essentially the same.
The mixing entropy formula derived in the previous problem actually applies to any ideal gas, and to some dense gases, liquids, and solids as well. For the denser systems, we have to assume that the two types of molecules are the same size and that molecules of different types interact with each other in the same way as molecules of the same type (same forces, etc.). Such a system is called an ideal mixture. Explain why, for an ideal mixture, the mixing entropy is given by
where is the total number of molecules and is the number of molecules of type . Use Stirling's approximation to show that this expression is the same as the result of the previous problem when both and are large.
Use a computer to reproduce the table and graph in Figure: two Einstein solids, each containing three harmonic oscillators, with a total of six units of energy. Then modify the table and graph to show the case where one Einstein solid contains six harmonic oscillators and the other contains four harmonic oscillators (with the total number of energy units still equal to six). Assuming that all microstates are equally likely, what is the most probable macrostate, and what is its probability? What is the least probable macrostate, and what is its probability?
Consider again the system of two large, identical Einstein solids treated in Problem .
(a) For the case , compute the entropy of this system (in terms of Boltzmann's constant), assuming that all of the microstates are allowed. (This is the system's entropy over long time scales.)
(b) Compute the entropy again, assuming that the system is in its most likely macro state. (This is the system's entropy over short time scales, except when there is a large and unlikely fluctuation away from the most likely macro state.)
(c) Is the issue of time scales really relevant to the entropy of this system?
(d) Suppose that, at a moment when the system is near its most likely macro state, you suddenly insert a partition between the solids so that they can no longer exchange energy. Now, even over long time scales, the entropy is given by your answer to part (b). Since this number is less than your answer to part (a), you have, in a sense, caused a violation of the second law of thermodynamics. Is this violation significant? Should we lose any sleep over it?
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