0
$\begingroup$

Kittel and Kroemer derive the pressure of a statistical state in the following way:

They assume a volume compression of a system such that the quantum state of the system is maintained at all times; thus, the entropy $(\sigma)$ is constant in the process of compression. Now let the energy of the system with state $s$ be $\epsilon_s$, then

$$\epsilon_s(V-\Delta V)=\epsilon_s(V)-\frac{d\epsilon_s}{dV}\Delta V+...$$

Since the work done on the system is equal to the change in energy of the system, $$U(V-\Delta V)-U(V)=\Delta U= -\frac{d\epsilon_s}{dV}\Delta V$$

In terms of pressure, $p_s$ on the state we can write $\Delta U = p_s\Delta V$, thus getting

$$p_s=-\frac{d\epsilon_s}{dV}$$

Defining average pressure, $p=\langle p_s\rangle $

$$p=-\bigg(\frac{\partial E}{\partial V }\bigg)_{\displaystyle\sigma}$$

where $E$ is the average energy of the system.

Now, it makes sense to me to talk about average energy, since it's just the sum of all possible energies divided by the number of them. The same would have been the case with pressure, but the fact that we are defining it in terms of such precise and singular conditions (isentropic compression of one particular state at a time) makes me have trouble understanding its physical meaning specifically, on how the actual pressure measured is related to $p$, given the specific condition to measure $p_s$.

$\endgroup$
9
  • $\begingroup$Pretty sure I don't understand what bothers you, but just in case: the pressure is defined by the isentropic change of energy because we want to obtain the energy change due to work on the system, not due to some temperature change or heat exchange. For a pure state, this would correspond to a system for which the change of energy is due to a change of the energy level spacings and not to a change of state (due to thermal fluctuations). Then, we simply average over all states and let statistical mechanics do its magic. But the important part is really that such definition clearly extract only$\endgroup$
    – Syrocco
    Commented13 hours ago
  • $\begingroup$... change of energy due to work. Which is the definition of the pressure in thermodynamics. Namely that chznge of energy can be due to change of entropy (~ heat) or change of volume in simple system. The later being the only we can directly use to extract work from the system$\endgroup$
    – Syrocco
    Commented13 hours ago
  • $\begingroup$@Syrocco If we compare the average values with the ones in quantum mechanics, then let a system have 3 discrete states with equal probability. Now, each time we will measure the system to be in one of these states, and based on that, we can get an average of the properties of the system, like its energy. But this average energy might not be something that we can actually measure, since it might not be an eigenvalue of the system. Now, in stat mech, consider many different states of a system, probable ones being only the ones that are sharply peaked near the one with maximum entropy.$\endgroup$Commented12 hours ago
  • $\begingroup$Since the states can change at each moment in time, so will energy, thus leading to the idea of average energy. But, probable states are so sharply peaked, the measure of fluctuation in energy will be negligibly small, giving us a single energy value. But when we talk about pressure, again, the states are changing all the time, the pressure will change too, hence again we can get a sharply defined average pressure. Now, in "reality", there will again be pressure fluctuations, imagine a gas filled balloon, it will hence be contracting and expanding ever so slightly. Is this correct?$\endgroup$Commented12 hours ago
  • $\begingroup$Again, not sure I follow you, but concerning your last sentence, yes, the pressure is a random variable in most cases$\endgroup$
    – Syrocco
    Commented5 hours ago

0

Start asking to get answers

Find the answer to your question by asking.

Ask question

Explore related questions

See similar questions with these tags.