Chapter 3: Q. 3.19 (page 107)
Fill in the missing algebraic steps to derive equations 3.30, 3.31, and 3.33.
Short Answer
Thus the equations are derived to fill the missing steps.
Chapter 3: Q. 3.19 (page 107)
Fill in the missing algebraic steps to derive equations 3.30, 3.31, and 3.33.
Thus the equations are derived to fill the missing steps.
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Get started for freePolymers, like rubber, are made of very long molecules, usually tangled up in a configuration that has lots of entropy. As a very crude model of a rubber band, consider a chain of N links, each of length (see Figure 3.17). Imagine that each link has only two possible states, pointing either left or right. The total length L of the rubber band is the net displacement from the beginning of the first link to the end of the last link.
(a) Find an expression for the entropy of this system in terms of N and NR, the number of links pointing to the right.
(b) Write down a formula for L in terms of N and NR.
(c) For a one-dimensional system such as this, the length L is analogous to the volume V of a three-dimensional system. Similarly, the pressure P is replaced by the tension force F. Taking F to be positive when the rubber band is pulling inward, write down and explain the appropriate thermodynamic identity for this system.
(d) Using the thermodynamic identity, you can now express the tension force F in terms of a partial derivative of the entropy. From this expression, compute the tension in terms of L, T, N, and .
(e) Show that when L << N, the tension force is directly proportional to L (Hooke's law).
(f) Discuss the dependence of the tension force on temperature. If you increase the temperature of a rubber band, does it tend to expand or contract? Does this behavior make sense?
(g) Suppose that you hold a relaxed rubber band in both hands and suddenly stretch it. Would you expect its temperature to increase or decrease? Explain. Test your prediction with a real rubber band (preferably a fairly heavy one with lots of stretch), using your lips or forehead as a thermometer. (Hint: The entropy you computed in part (a) is not the total entropy of the rubber band. There is additional entropy associated with the vibrational energy of the molecules; this entropy depends on U but is approximately independent of L.)
The results of either of the two preceding problems can also be applied to the vibrational motions of gas molecules. Looking only at the vibrational contribution to the heat capacity graph for shown in Figure 1.13, estimate the value of for the vibrational motion of an molecule.
Use a computer to study the entropy, temperature, and heat capacity of an Einstein solid, as follows. Let the solid contain 50 oscillators (initially), and from 0 to 100 units of energy. Make a table, analogous to Table 3.2, in which each row represents a different value for the energy. Use separate columns for the energy, multiplicity, entropy, temperature, and heat capacity. To calculate the temperature, evaluate for two nearby rows in the table. (Recall that for some constant .) The heat capacity can be computed in a similar way. The first few rows of the table should look something like this:
(In this table I have computed derivatives using a "centered-difference" approximation. For example, the temperature is computed as .) Make a graph of entropy vs. energy and a graph of heat capacity vs. temperature. Then change the number of oscillators to 5000 (to "dilute" the system and look at lower temperatures), and again make a graph of heat capacity vs. temperature. Discuss your prediction for the heat capacity, and compare it to the data for lead, aluminum, and diamond shown in Figure 1.14. Estimate the numerical value of in electron-volts, for each of those real solids.
Suppose you have a mixture of gases (such as air, a mixture of nitrogen and oxygen). The mole fraction of any species is defined as the fraction of all the molecules that belong to that species: . The partial pressure of species is then defined as the corresponding fraction of the total pressure: . Assuming that the mixture of gases is ideal, argue that the chemical potential of species in this system is the same as if the other gases were not present, at a fixed partial pressure .
Starting with the result of Problem 2.17, find a formula for the temperature of an Einstein solid in the limit . Solve for the energy as a function of temperature to obtain (where is the size of an energy unit).
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