PHYS 213 discussion problem set 2: Entropy, energy,

internal energy, and heat capacity

Introduction
Entropy of volume
The definition of entropy for a given macrostate is S = k ln Ω, where k = 1.380649 × 10−23 J/K,
and Ω is the number of microstates in the macrostate. As of 2019, the definition of k is exact, since
it is one of the bases of our units. As an example of computing entropy for a physical system, we
compute the entropy of a particle confined to a volume V .

Internal energy, entropy, temperature, and heat capacity

For constant volume, there are a number of useful relationships between these quantities:

• First law: dU = dQ − pdV .

• Temperature definition: dS
dU
= 1T.

• Heat capacity definition: C = dTdQ.

One thing you should be careful about is the difference between a differential dU and a total change
∆U . The relationship is that
∫ Qf ∫ Vf
∆U = dQ − pdV. (1)
Qi Vi

When the volume is constant, the second integral is always zero, because Vi = Vf . This means that
dU = dQ. You can compute changes in entropy and internal energy by integrating the equations,
for example,
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dS =dU
T
dU = CV dT
CV
dS = dT
∫ T
CV
∆S = dT
T

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1 Volume entropy - Groups B and D
In this problem, we will study the entropy for an idealized gas in a volume V , with temperature
constant. In such a system, the number of places for a single particle to be in a volume V is
Ω1 = AV . A may depend on the specific gas and temperature, but we’ll find out that it doesn’t
matter for computing changes in entropy. We often are not concerned too much with the total
entropy, but instead with changes in entropy.

1.1 N particles
What is the number of ways to distribute N particles ΩN ? Assume the particles don’t interact in
any way.

1.2 Entropy
Derive a formula for the entropy of N particles. Use logarithm rules to simplify the expression.

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1.3 Volume expansion
Now compute the change in entropy from a gas expanding, at a constant temperature, from Vi to
Vf . Show that A cancels out in the change in entropy, and use logarithm rules to simplify the
answer.

1.4 Computation.
Use the relationship you derived above to compute the change in entropy of a gas of 1023 particles
as it expands from a volume of 1 m 3 to 1.5 m3. Use the definition of entropy S = k ln Ω to
determine by what factor the number of microstates increased on that expansion. Leave the number
as an exponential; it will probably overflow your calculator.

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2 Finding equilibrium between two blocks - Groups C and E
In this problem we consider heat transfer in the situation where the volume is constant, but energy
can be transferred between two blocks.
A block of aluminum is heated to 100 ◦C by placing it in boiling water, and placed in contact
with a block of gold, which is at room temperature of 20 ◦C. Assume that their volumes do not
change, but heat energy can only flow between the two blocks and not out to the environment.

2.1 Equilibrium condition

Find the equilibrium condition by maximizing the total entropy of the system.

• Stot = S Al(UAl) + S Au(UAu)

.dSX Σ 1
• Definition of temperature for block X: dU V,N = TX

• Energy conservation: UAl + UAu = A, where A is some constant.

2.2 In equilibrium?
At the initial condition, do the two blocks satisfy the equilibrium condition? Are they in equilib-
rium or out of equilibrium?

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2.3 Final temperature
Derive a formula for the final temperature in equilibrium, using conservation of energy and the
equilibrium condition from 2.1. It will be a function of the heat capacities and initial temperatures
of the two blocks.

2.4 Application
In tables, we typically list the heat capacity per g or per mol. Pay attention to the units!
Material Specific heat capacity (J/g K)
Au 0.129
Al 0.900
Suppose that there is 1 kg of Al and 1 kg of Au. Using the formula in 2.3, would the final
temperature be closer to the Au initial temperature or the Al initial temperature? Give a reason
why.

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3 Heat capacity, internal energy, and entropy - Groups A and
F
Heat capacity is defined as the amount of heat it requires to change the temperature: C = dQ
dT
.

3.1 Change in internal energy U

Use the first law of thermodynamics dU = dQ−pdV and the definition of heat capacity to compute
a formula for the change in internal energy ∆U when the temperature changes from Ti to Tf at
constant volume. You will need an integral.

3.2 Change in entropy

Find a formula for ∆S in terms of C, using the definition dSdU = 1/T .

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3.3 Non-constant heat capacity
Suppose a block has a heat capacity CV (T ) = A + BT . Compute formulas for the change in
internal energy and entropy for this material, if we start at Ti and add heat until it is at Tf .

3.4 Change in entropy

For A = 1 J/K and B = 0.02 J/K2, Ti = 300 K, Tf = 301 K.

• Compute the change in entropy in J/K.

• Using the definition of entropy S = k ln Ω, derive a formula for the ratio Ω(TF )/Ω(Ti),
and evaluate the number in the exponential. Your calculator may not be able to handle the
number.

• Give an explanation for why the higher temperature state has more microstates.