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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

A cylinder contains one liter of air at room temperature ( 300K) and atmospheric pressure 105N/m2. At one end of the cylinder is a massless piston, whose surface area is 0.01m2. Suppose that you push the piston in very suddenly, exerting a force of 2000N. The piston moves only one millimeter, before it is stopped by an immovable barrier of some sort.

(a) How much work have you done on this system?

(b) How much heat has been added to the gas?

(c) Assuming that all the energy added goes into the gas (not the piston or cylinder walls), by how much does the internal energy of the gas increase?

(d) Use the thermodynamic identity to calculate the change in the entropy of the gas (once it has again reached equilibrium).

Use the thermodynamic identity to derive the heat capacity formula

CV=T∂S∂TV

which is occasionally more convenient than the more familiar expression in terms of U. Then derive a similar formula for CP, by first writing dHin terms of dSand dP.

Consider an ideal two-state electronic paramagnet such as DPPH, with μ=μB. In the experiment described above, the magnetic field strength was 2.06T and the minimum temperature was 2.2K. Calculate the energy, magnetization, and entropy of this system, expressing each quantity as a fraction of its maximum possible value. What would the experimenters have had to do to attain99% of the maximum possible magnetization?

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 â„“(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 â„“.
(e) Show that when L << Nâ„“, 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.)

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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