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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.

Short Answer

Expert verified

The table can be prepared as:

The graphs can be made as:

For 50 oscillations

For 5000 oscillations

The values of εare:

εlead=6.875×103eVεaluminium=2.587×102eVεdiamond=0.19233eV

Step by step solution

01

Given Information

The given Einstein solid contains 50 oscillators from 0 to 100 units of energy.

That is,

N=50q=1to100

U=qϵ

02

Calculation for table values

The entropy of the system is given as:

Sk=lnΩSk=lnq+N-1qN-1

The temperature is given as:

1T=SUT=ΔUΔST=Δ(εq)Δ(klnΩ)kTϵ=Δ(q)Δ(lnΩ)

Heat capacity per oscillation is given as:

CN=ΔUNΔTCN=Δ(εq)NΔΔ(εq)Δ(klnΩ)CNk=Δ(q)NΔΔ(q)Δ(lnΩ)

The table consisting of entropy, temperature, and heat capacity of an Einstein solid for 50 oscillations with 0 to 100 units of energy can be prepared as follows:

03

Graph

The graphs of entropy vs energy and heat capacity vs temperature can be sketched as follows:

For 50 oscillations:

The graph of entropy vs energy can be made as:

The graph of heat capacity vs temperature can be made as:

For 5000 oscillations:

The graph of entropy vs energy can be made as:

The graph of heat capacity vs temperature can be made as:

The heat capacity is substantially smaller than the values in figure 1.14, since, for 5000 oscillations with the same units of energy, the energy is lowered, lowering the system's temperature.

04

Calculation of ε

For q=1,Ω=1

Solving for ε,we get,

U=ϵqε=Uqϵ=Tk(lnΩ)qε=kT

For lead, heat capacity is maximum at T=80K

εlead=kTεlead=1.38×10-23×80εlead=1.1×10-21Jεlead=6.875×10-3eV

For aluminum heat capacity is maximum at T=300K

εaluminum=kTεaluminum=1.38×10-23×300εaluminum=4.14×10-21Jεaluminum=2.587×10-2eV

For diamond heat capacity is maximum at T=2230K

εdiamond=kTεdiamond=1.38×10-23×2230εdiamond=3.0774×10-20Jεdiamond=0.19233eV

05

Final answer

The table of the values can be prepared as:

The graphs can be prepared as:

For 50 oscillations:

For 5000 oscillations:

The value of εare:

ϵlead=6.875×103eVϵaluminium=2.587×102eVϵdiamond=0.19233eV

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Most popular questions from this chapter

As shown in Figure 1.14, the heat capacity of diamond near room temperature is approximately linear in T. Extrapolate this function up to 500K, and estimate the change in entropy of a mole of diamond as its temperature is raised from298K to 500K. Add on the tabulated value at298K (from the back of this book) to obtain S(500K).

In Problem 2.18 you showed that the multiplicity of an Einstein solid containing N oscillators and q energy units is approximately

Ω(N,q)q+Nqqq+NNN

(a) Starting with this formula, find an expression for the entropy of an Einstein solid as a function of N and q. Explain why the factors omitted from the formula have no effect on the entropy, when N and q are large.

(b) Use the result of part (a) to calculate the temperature of an Einstein solid as a function of its energy. (The energy is U=qϵ, where ϵis a constant.) Be sure to simplify your result as much as possible.

(c) Invert the relation you found in part (b) to find the energy as a function of temperature, then differentiate to find a formula for the heat capacity.

(d) Show that, in the limit T, the heat capacity is C=Nk. (Hint: When x is very small, ex1+x.) Is this the result you would expect? Explain.

(e) Make a graph (possibly using a computer) of the result of part (c). To avoid awkward numerical factors, plot C/Nkvs. the dimensionless variable t=kT/ϵ, for t in the range from 0 to about 2. Discuss your prediction for the heat capacity at low temperature, comparing to the data for lead, aluminum, and diamond shown in Figure 1.14. Estimate the value of ϵ, in electron-volts, for each of those real solids.

(f) Derive a more accurate approximation for the heat capacity at high temperatures, by keeping terms through x3 in the expansions of the exponentials and then carefully expanding the denominator and multiplying everything out. Throw away terms that will be smaller than(ϵ/kT)2 in the final answer. When the smoke clears, you should find C=Nk1-112(ϵ/kT)2.

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).

In solid carbon monoxide, each CO molecule has two possible orientations: CO or OC. Assuming that these orientations are completely random (not quite true but close), calculate the residual entropy of a mole of carbon monoxide.

An ice cube (mass 30g)0°Cis left sitting on the kitchen table, where it gradually melts. The temperature in the kitchen is 25°C.

(a) Calculate the change in the entropy of the ice cube as it melts into water at 0°C. (Don't worry about the fact that the volume changes somewhat.)

(b) Calculate the change in the entropy of the water (from the melted ice) as its temperature rises from 0°Cto 25°C.

(c) Calculate the change in the entropy of the kitchen as it gives up heat to the melting ice/water.

(d) Calculate the net change in the entropy of the universe during this process. Is the net change positive, negative, or zero? Is this what you would expect?

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