Interpretation of Temperature

Question

In differential form, the First Law of thermodynamics can be phrased as

$$ dU = T\,dS - P\,dV + \sum_{j = 1}^N \mu_j\, dn_j, \quad (1)$$

or equivalently as

$$ dU = \left( \frac{\partial U}{\partial S}\right)dS - \left( \frac{\partial U}{\partial V} \right) dV + \sum_{j = 1}^N \left(\frac{\partial U}{\partial n_j}\right)dn_j. \quad (2)$$

This latter expression shows how each of the intensive variables of the system (i.e. temperature, pressure and chemical potential) represent something akin to energy per unit extensive quantity. For example, one can think of pressure as the energy of the system per unit volume. Likewise, one can consider chemical potential to be the energy of the system per unit particle. Now, the analogy seems to break down when one tries to think of temperature in the same way. The temperature is… the system energy per unit of entropy? What the heck does that mean?

Answer 1

The analogy does not break down at all, on the contrary it means exactly that: temperature is the system's internal energy per unit entropy increase while the other extensive parameters are kept constant. Entropy is the active agent of thermal interaction whose transport from one potential (temperature) to another is the reason for work performed, just as gravitational mass or electric charge are the agents of gravitational work or electric work, resp., mass or charge moves from one potential to another.

Answer 2

The answers saying that temperature is the energy per unit entropy are fine, but I think you must have already considered this and found it unsatisfying. Let me try to develop some intuition about entropy (which is a minefield, I know). Entropy is roughly proportional to the number of degrees of freedom or, more colloquially, with the number of moving parts.

For instance, for a molecule with N rotatable bonds and 3 accessible rotation states for each bond, the conformational entropy is $S = k \ln (3^N) = kN \ln(3)$. This is consistent with the idea that the entropy is proportional to the number of moving parts (in this case, rotatable bonds).

So, we can think of temperature as being roughly like the amount energy per degree of freedom or the amount of energy per moving part of the object.

Does this intuitive picture work? Let's say we have a small solid object, like a block of iron. Compared to a larger block of iron, it has few degrees of freedom. If the small block and large block have the same energy, the small block has a higher temperature than the large block. So, for simple situations like this, the picture gives the right intuition.

Answer 3

As hyportnex's nice answer says, there is nothing wrong with this analogy at all. The thermodynamic definition of temperature is, $$T = \frac{\partial U}{\partial S} $$ The fact that this is an incredibly weird and unintuitive statement is actually one of the reasons that thermodynamics is so powerful; it tells us surprising things about the behavior of the world in a truly fundamental way.

Just to build off of why there is some rationality behind the connection of entropy and temperature, one definition of the entropy in thermodynamics, attributed to Rudolf Clausius, is, $$ dS = \frac{\delta q_{rev}}{T}$$ where $\delta q_{rev}$ is the inexact differential for heat transfer in a reversible process. By doing some further work, you can arrive at the Clausius inequality for any process, $$ dS \geq \frac{\delta q}{T}$$ The reason that I bring this up is that the only things you need to argue that heat flows from hotter bodies to colder ones are the Clausius inequality and the second law of thermodynamics. This means that because of the spontaneity condition $dS \geq 0$ for an isolated system coming to equilibrium, we will always have changes in temperature that correspond to our physical intuition; heat will flow into the system if it is colder than the surroundings and out of it if it is warmer.