Alex Heinrich

PHYS 533
Homework 7
03/01/2024

3.5-1: Exact differentials and equations of state

Determine if each of the listed pairs of equations of state are compatible. If so, find the fundamental
relation.

a. 𝑢 = 𝑎𝑃𝑣, 𝑃𝑣 = 𝑏𝑇

Since our intensive parameters are defined as integrating factors, they must satisfy the following.
d𝑠 = d𝑢 + d𝑣 ≡ d𝑢 + d𝑣
=
Fundamental relations can be derived by integration. I will quote some convenient generalizations
for two and three dimensions for later application.
𝐹 =𝐹 +∫ (𝑥̅ , 𝑦) d𝑥̅ + ∫ (0, 𝑦) d𝑦
𝐹 =𝐹 +∫ (𝑥̅ , 𝑦, 𝑧) d𝑥̅ + ∫ (0, 𝑦, 𝑧) d𝑦 + ∫ (0,0, 𝑧̅)d𝑧̅
We will test each pair of equations with these in mind, beginning with the extraction of our
integrating factors from the given equations.
= , = =
The resulting partial derivates are easy.
=−
=0
Hence, the equations of state are not compatible.

b. 𝑢 = 𝑎𝑃𝑣 , 𝑃𝑣 = 𝑏𝑇

We will begin by extracting our integrating factors.

= , = =
The resulting partial derivates are easy and indicate that the equations of state are compatible.
=0
=0
We can derive the fundamental relation by integration, absorbing some constants of integration
into 𝑠 .
d𝑠 = d𝑢 + d𝑣
𝑠 =𝑠 +∫ d𝑢 + ∫ d𝑣

= 𝑠 + 𝑎𝑏 ln −
 c. 𝑃 = , 𝑇=

We will begin by extracting our integrating factors.

= = , =
The resulting partial derivates are easy and indicate that the equations of state are compatible.
=𝑏
=𝑏
We can derive the fundamental relation by integration, absorbing some constants of integration
into 𝑠 .
d𝑠 = d𝑢 + d𝑣
𝑠 =𝑠 +∫ d𝑢 + ∫ d𝑣
=𝑠 +∫ d𝑢 + ∫ 𝑏𝑣 d𝑢 + ∫ d𝑣

= 𝑠 + 𝑎 ln + 𝑏𝑢𝑣 + 𝑐 ln

3.7-1: Differentials of extensive parameters

For the rubber band model, calculate the fractional change in 𝐿 − 𝐿 that results from an increase d𝑇 in
temperature at constant tension. Express the result in terms of the length and temperature.

In the rubber band model, observations of experiments and considerations of exact differentials lead to
the following equations for rest length 𝐿 , maximum length 𝐿 , tension 𝒯, and constants 𝑏 and 𝑐.
𝒯
d𝑆 = d𝑈 − d𝐿, 𝑇= , 𝒯 = 𝑏𝑇
We can rearrange the equation for tension to determine the differential for 𝐿 − 𝐿 .
𝐿−𝐿 = 𝒯
( ) ( )
d(𝐿 − 𝐿 ) = d𝑇 + d𝒯
𝒯
=− 𝒯 d𝑇 + d𝒯
=− 𝑏𝑇 d𝑇 + d𝒯
𝒯
=− d𝑇 + d𝒯
𝒯
The fractional change follows simply.
( ) 𝒯
=− +
𝒯
Finally, constant tension implies that d𝒯 = 0
( )
=−
3.7-2: Constant temperature and the first law of thermodynamics
A rubber band is stretched by an amount d𝐿 at constant temperature. Calculate the differential work and
heat transfer to the rubber band. How are these related and why?

As before, we will begin by recalling the fundamental relation for the rubber band model.
𝒯
d𝑆 = d𝑈 − d𝐿, 𝑇= , 𝒯 = 𝑏𝑇
Since heat and work are related to internal energy by the first law of thermodynamics, we will use the
information above to derive the differential for internal energy.
d𝑈 = d𝑇 + d𝒯
𝒯
= 𝑐𝐿 d𝑇
= đ𝑄 + đ𝑊
At constant temperature, this result implies d𝑈 = 0, so we can anticipate đ𝑄 + đ𝑊 = 0. Since there are
no changes to mole number or non-quasistatic processes, our heat transfer is proportional to the
change in entropy. We will apply the relations above to determine this heat explicitly.
đ𝑄 = 𝑇 d𝑆
𝒯
=𝑇 d𝑈 − d𝐿
𝒯
=𝑇 d𝑇 − d𝐿
= −𝒯 d𝐿
= −𝑏𝑇 d𝐿
The work done is proportional to the change in length. To determine the full functional form, we will
first consider the differentials for internal energy in typical cases in contrast to the rubber band model.
d𝑈 = 𝑇 d𝑆 − 𝑃 d𝑉
= 𝑇 d𝑆 + 𝒯 d𝐿
This implies that our work is đ𝑊 = 𝒯 d𝐿, rather than đ𝑊 = −𝑃 d𝑉.
đ𝑊 = 𝒯 d𝐿
= 𝑏𝑇 d𝐿
The work and heat transferred sum to zero as anticipated by comparing d𝑈 to the first law under the
condition of constant temperature.

3.7-3: Deriving consistent equations of state

If the energy of the unstretched rubber band were found to increase quadratically with temperature,
such that 𝑈 = 𝑐𝐿 𝑇 , would 𝒯 = 𝑏𝑇 require alteration?

Experimental observations indicated that tension increases with temperature at constant length. We
will represent this dependence by 𝒯 ∝ 𝑇 for some unknown value 𝑛.
𝒯
d𝑆 = d𝑈 − d𝐿

= d𝑈 − 𝑏𝑇 d𝐿
In order for our equations of state to be consistent, they must be integrating factors of our differential
for entropy.
=0
( )/
𝑏𝑇 =𝑏
( )/
=𝑏 ( )( )/

In order for this to agree with our known equation of state, we must have 𝑛 = 1. Hence, our tension is
linear in temperature, so no change to our equations of state is needed.

3.9-2: An exercise in exponentials and logarithms

Corroborate the following equation for a multicomponent simple ideal gas, showing that both the right-
hand and left-hand members of the equation equal −𝑇/𝑐̅𝑉, where 𝑐̅ ≡ ∑(𝑐 𝑁 ) /𝑁.
=−
, ,

The equation presented is a necessary condition for exact differentials in the energy representation.
d𝑈 = d𝑆 + d𝑉 + ∑ d𝑁
≡ 𝑇 d𝑆 − 𝑃 d𝑉 + ∑ (𝜇 d𝑁 )
In order to find 𝑇 and 𝑃 in this representation, we can use the postulates of thermodynamics to extract
an equation for 𝑈 from our fundamental relation in the entropy representation.
𝑆 = 𝑆 + ∑ (𝑐 𝑁 ) 𝑅 ln + ∑ 𝑁 𝑅 ln
𝑈 = exp ∑ ( )
𝑆−∑ 𝑁 𝑅 ln + ln(𝑈 ) − 𝑆
Since we want to take partial derivatives of this equation, it will benefit us to rewrite 𝑈.
𝑈 = exp ∑ ( )
𝑆−∑ 𝑅𝑁 ln + 𝑓(𝑁 )
∑ ( ( / ))
= exp ∑ ( )
exp ∑ ( )
+ 𝑓(𝑁 )
( )∑ ( ) ∑ ( ( ))
= exp ∑ ( )
exp ∑ ( )
exp ∑ ( )
+ 𝑓(𝑁 )
∑ ( )
∑ ( ( ))
= exp ∑ ( )
exp(ln(𝑉)) ∑ ( ) exp ∑ ( )
+ 𝑓(𝑁 )
∑ ( )
∑ ( ( ))
= exp ∑ ( )
𝑉 ∑ ( ) exp ∑ ( )
+ 𝑓(𝑁 )
Here, 𝑓(𝑁 ) is a function of our mole numbers that contains some of our initial conditions. We will
proceed by finding our intensive parameters in this representation.
𝑇≡
∑ ( )
∑ ( ( ))
= exp ∑ ( )
𝑉 ∑ ( ) exp ∑ ( )
∑ ( )
∑ ( ( ))
= ∑ ( )
exp ∑ ( )
𝑉 ∑ ( ) exp ∑ ( )
= ∑ ( )
= ̅
 𝑃≡−
∑ ( )
∑ ( ( ))
=− exp ∑ ( )
𝑉 ∑ ( ) exp ∑ ( )
∑ ( )
∑ ( ) ∑ ( ( ))
= ∑ ( )
exp ∑ ( )
𝑉 ∑ ( ) exp ∑ ( )
∑ ( )
= ∑ ( )
∑ ( )
= ∑ ( )
= ̅
This allows us to compute the second partial derivates cleanly.
− =− ̅
=− ̅
= − ̅

= ̅
= ̅
=− ̅ ̅
=− ̅ ̅
= − ̅