What does the relation for temperature dE/dS=T mean physically?

In summary, the equation dS/dE = 1/T has a physical interpretation as temperature being a measure of the increase in disorder when energy is added to a system. This can be seen in the limiting cases of T approaching 0 and T approaching infinity, where the change in entropy for a small change in energy is very different. This equation also holds for more complex systems.
  • #1
Polyrhythmic
343
0
The only reason I can think of is: By defining [itex]S=k_b \log \Omega[/itex], it just works out; for an ideal gas as well as for other systems (that I can't come up with right now).

[itex]\frac{dS}{dE}=\frac {1}{T(E,...)}\,[/itex] states that temperature is a measure of the increase in entropy when some energy is added to a system. Is there a physical interpretation of this quantity other than the above?
 
Science news on Phys.org
  • #2
dS/dE=1/T is not correct if you mean a total derivative. Generally,

dE = TdS + Jdx + μdN

[where the bolds are column matrices: J and x are the generalized forces and displacements (respectively); μ and N are the various chemical potentials and number of molecules of each chemical (respectively). Two vectors next to each other means the dot product.]

So really the equation you're wondering about is

[tex]T = \frac{\partial E}{\partial S}\bigg|_{\mathbf{x, N}} [/tex]
or
[tex]\frac{1}{T} = \frac{\partial S}{\partial E}\bigg|_{\mathbf{x, N}} [/tex]

Anyway, interpreting any equation with entropy can be confusing. In many interpretations that involve S, you can think of it as "a measure of disorder."

What those equations mean kind of falls right out: temperature is given by the change in energy that results from an infinitesimal change in entropy divided by that change in entropy, keeping the number of particles and displacements (e.g. volume) constant. [Not very satisfying, right?]
One possible example to help make this intuitive uses the Third Law, which states that entropy approaches zero as temperature approaches zero. As such, we'll look at limiting cases.

As an example, let's look at a microcanonical ensemble of N "impurities," each with two energy levels (for example, N stationary spin 1/2 particles in a magnetic field). At a finite temperature, there will be a mixture of excited impurities and ground-state impurities and their distribution will be given by the normal Boltzmann factor exp -E/(kT). So as temperature goes to ∞, half will be excited and half will be ground-state, whereas temperature going to 0 ensures they will all be in the ground state.

Holding x and N fixed, let's make a small (positive) change in the energy of this microcanonical ensemble and observe what happens to the entropy in two limiting cases, T→0 and T→∞. This corresponds to the expression for 1/T. To make this small positive change in energy, we would take a ground state impurity and flip it into the excited state. Also remember that we are considering "the thermodynamic limit" N→∞.

In the T→∞ limit
Roughly half of the impurities are excited and the other half are in ground state. Taking one impurity and exciting it wouldn't make that much of a change in how "disordered" the system is... If we looked at a picture of N/2 excited impurities and N/2 ground-state impurities, you probably couldn't tell it apart from a picture of N/2+1 excited impurities and N/2-1 ground-state impurities--they're equally disorderly.

This is the intuitive way of talking about entropy. In terms of microstates, there are roughly the same number of microstates with N/2 excited impurities as N/2+1 excited impurities.

So the change in "disorder" and hence the change in entropy for an infinitesimal change in energy is negligible in the limit T→∞, consistent with the equation you asked about.

In the T→0 limit
All the impurities are in ground state. There is only one microstate such that all the particles are in the ground state! If we excite one impurity, there will be N possible microstates. Hence the change in entropy is on the order of log(N), which approaches ∞ in the thermodynamic limit. Intuitively, even for a huge number of particles, you'd easily be able to see the difference between a picture with N ground state impurities and 0 excited impurities and a picture with N-1 ground state impurities and 1 excited impurity. If all of them are ground state, it is much more orderly. So the change in entropy is huge for an infinitesimal change in energy in the limit T→0, again consistent with the equation you asked about.Similar arguments hold for intermediate values of T, and for more complicated/less idealized systems.(If you wanted to make my explanation a little more rigorous, you would want to avoid having the microstate with N+1 excited impurities, since this actually implies a negative value for T [headscratcher alert]. So in that case, instead of exciting one groundstate impurity, it would be better to relax one excited impurity--you'd get a negative on top and bottom of the partial derivative and everything else would still hold. Just a technical point.)
 
Last edited:

1. What is the physical meaning of the temperature relation dE/dS = T?

The temperature relation dE/dS = T, also known as the Clausius-Clapeyron relation, is a fundamental equation in thermodynamics that relates the change in energy (dE) to the change in entropy (dS) at a constant temperature (T). It essentially describes the relationship between heat and work in a system, and provides a way to calculate the temperature at which a substance will undergo a phase change, such as melting or boiling.

2. How does the temperature relation dE/dS = T relate to the laws of thermodynamics?

The temperature relation dE/dS = T is a direct consequence of the second law of thermodynamics, which states that the total entropy of an isolated system will always increase over time. In other words, the temperature relation describes the direction in which energy will flow in a system in order to maintain this increase in entropy.

3. Can the temperature relation dE/dS = T be applied to all systems?

Yes, the temperature relation dE/dS = T is a universal equation that applies to all systems, regardless of their size or complexity. It is a fundamental principle in thermodynamics and is used to describe the behavior of everything from a small molecule to an entire galaxy.

4. How is the temperature relation dE/dS = T used in practical applications?

The temperature relation dE/dS = T is used in a variety of practical applications, such as in the design of heat engines and refrigeration systems. It is also used in the study of phase transitions and the behavior of materials at extreme temperatures. Additionally, it is a key concept in the field of chemical thermodynamics, where it is used to predict the behavior of chemical reactions.

5. Is there a limit to the accuracy of the temperature relation dE/dS = T?

While the temperature relation dE/dS = T is a highly accurate and useful equation, it does have limitations. One major limitation is that it assumes that the system is in a state of equilibrium, meaning that all the components are at the same temperature. This may not always be the case in real-world situations, so the relation may not provide exact results in all cases.

Similar threads

Replies
9
Views
6K
Replies
9
Views
1K
Replies
21
Views
4K
Replies
19
Views
1K
Replies
1
Views
741
  • Thermodynamics
Replies
4
Views
1K
Replies
1
Views
1K
  • Thermodynamics
Replies
1
Views
734
Replies
22
Views
2K
Back
Top