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According to the Sackur-Tetrode equation, the entropy of a monatomic ideal gas can become negative when its temperature (and hence its energy) is sufficiently low. Of course this is absurd, so the Sackur-Tetrode equation must be invalid at very low temperatures. Suppose you start with a sample of helium at room temperature and atmospheric pressure, then lower the temperature holding the density fixed. Pretend that the helium remains a gas and does not liquefy. Below what temperature would the Sackur-Tetrode equation predict that Sis negative? (The behavior of gases at very low temperatures is the main subject of Chapter 7.)

Short Answer

Expert verified

The critical temperature of helium at room temperature and atmospheric pressure isTcrit=0.01213.

Step by step solution

01

Step: 1 Getting degree of freedom:

By Sackur-Tetrode formulua for 3-dideal gas is

S=NklnVN4mU3Nh222+52

WhereVrepresents volume, Urepresents energy,Nrepresents the number of molecules, mrepresents the mass of a single molecule, and hrepresents Planck's constant. The logarithm term can go below-5/2if the energy Ufalls low enough, making Snegative. Because this is not conceivable, the Sackur-Tetrode equation must fail at low energies.

The monatomic gas of inernal energy is

U=f2NkT

Where, fis degree of freedom,the monatomic gas has localid="1650268768225" f=3.

localid="1650268764922" U=32NkT

02

Step: 2 Equating critical temperature:

Having an mole of helium and it cools.

The critical temperaature form as

52=lnVN4mUcrit3Nh232

substituting equation we get,

52=lnVN4m32NkTcrit3Nh23252=lnVN2mkTcrith232

Taking exponential on both sides,

As eln(a)=awe get,

e52=VN2mkTcrith2322mkTcrith2=NVe5223Tcrit=h22mkNVe5223

03

Step: 3 Finding critical temperature value:

The mole mass of helium is 4.0026gso, the molecule of mass helium is

m=Mass of one moleNumber of atoms one moleNAm=4.00261036.0221023m=6.6461027kg.

From ideal-gas law,the pressure of 1atm=101325Paand temperature of 300K.

The volume occupies one one mole is

V=nRTPV=8.31300101325V=0.0246m3.

Substituting the values of k=1.381023JK1and h=6.6261034Jsinto equation we get

Tcrit=6.6261034226.64610271.3810236.02210230.0246e5223Tcrit=0.01213

In reality, because helium liquefies at roughly 4K, formula appears to be valid for the region where helium is still a gas.

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Most popular questions from this chapter

This problem gives an alternative approach to estimating the width of the peak of the multiplicity function for a system of two large Einstein solids.

(a) Consider two identical Einstein solids, each with Noscillators, in thermal contact with each other. Suppose that the total number of energy units in the combined system is exactly 2N. How many different macrostates (that is, possible values for the total energy in the first solid) are there for this combined system?

(b) Use the result of Problem2.18to find an approximate expression for the total number of microstates for the combined system. (Hint: Treat the combined system as a single Einstein solid. Do not throw away factors of "large" numbers, since you will eventually be dividing two "very large" numbers that are nearly equal. Answer: 24N/8蟺狈.)

(c) The most likely macrostate for this system is (of course) the one in which the energy is shared equally between the two solids. Use the result of Problem 2.18to find an approximate expression for the multiplicity of this macrostate. (Answer:24N/(4蟺狈) .)

(d) You can get a rough idea of the "sharpness" of the multiplicity function by comparing your answers to parts (b) and (c). Part (c) tells you the height of the peak, while part (b) tells you the total area under the entire graph. As a very crude approximation, pretend that the peak's shape is rectangular. In this case, how wide would it be? Out of all the macrostates, what fraction have reasonably large probabilities? Evaluate this fraction numerically for the case N=1023.

Use a computer to reproduce the table and graph in Figure2.4: 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?

Suppose you flip four fair coins.

(a) Make a list of all the possible outcomes, as in Table 2.1.

(b) Make a list of all the different "macrostates" and their probabilities.

(c) Compute the multiplicity of each macrostate using the combinatorial formula 2.6, and check that these results agree with what you got by bruteforce counting.

How many possible arrangements are there for a deck of 52playing cards? (For simplicity, consider only the order of the cards, not whether they are turned upside-down, etc.) Suppose you start w e in the process? Express your answer both as a pure number (neglecting the factor of k) and in SI units. Is this entropy significant compared to the entropy associated with arranging thermal energy among the molecules in the cards?

Calculate the multiplicity of an Einstein solid with 30oscillators and 30units of energy. (Do not attempt to list all the microstates.)

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