Experimental measurements of heat capacities are often represented in reference works as empirical formulas. For graphite, a formula that works well over a fairly wide range of temperatures is (for one mole)

CP=a+bT-cT2

where a=16.86J/K,b=4.77×10-3J/K2, and c=8.54×105J·K. Suppose, then, that a mole of graphite is heated at constant pressure from 298Kto 500K. Calculate the increase in its entropy during this process. Add on the tabulated value of S(298K)(from the back of this book) to obtain S(500K).

Short Answer

Expert verified

ΔS=5.74JK-1

S(500)=12.329JK-1

Step by step solution

01

Explanation of Solution

Given:

The heat capacity for one mole of graphite is

CP=a+bT-cT2a=16.86JK-1b=4.77×10-3JK-2c=8.54×105JK

At 298Kthe entropy of a mole of graphite is 5.74JK-1.

Formula used:

The change in entropy is,ΔS=TiTfCP(T)TdT

02

Calculation

The change in entropy when the temperature changes from 298Kto 500K,

ΔS=TiTfa+bT-cT2TdTΔS=298K500KaT+b-cT3dT=alnT+bT+c2T2298K500K=16.86JK-1ln500+4.77×10-3JK-2×500+8.54×105JK2×5002-16.86JK-1ln298+4.77×10-3JK-2×298+8.54×105JK2×2982=6.589JK-1

At 500Kthe total entropy of graphite is,

S(500)=5.74JK-1+6.589JK-1

=12.329JK-1

03

Conclusion

The entropy changes ΔS=5.74JK-1and the total entropy at 500K is S(500)=12.329JK-1.

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Most popular questions from this chapter

Polymers, 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.)

Sketch (or use a computer to plot) a graph of the entropy of a two-state paramagnet as a function of temperature. Describe how this graph would change if you varied the magnetic field strength.

When the sun is high in the sky, it delivers approximately 1000 watts of power to each square meter of earth's surface. The temperature of the surface of the sun is about 6000K, while that of the earth is about 300K.

(a) Estimate the entropy created in one year by the flow of solar heat onto a square meter of the earth.

(b) Suppose you plant grass on this square meter of earth. Some people might argue that the growth of the grass (or of any other living thing) violates the second law of thermodynamics, because disorderly nutrients are converted into an orderly life form. How would you respond?

A liter of air, initially at room temperature and atmospheric pressure, is heated at constant pressure until it doubles in volume. Calculate the increase in its entropy during this process.

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 ΔU/ΔSfor two nearby rows in the table. (Recall that U=qϵfor some constant ϵ.) The heat capacity (ΔU/ΔT)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 .28is computed as 2/(7.15-0).) 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 εin electron-volts, for each of those real solids.

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