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What is the interpretation of $dE - TdS \leq 0$?

If I understand correctly this is the Helmholtz free energy: $$ dF = dE - TdS $$

I understand that if the process costs energy and this cannot be supplied this process will not be spontaneous. Does this equation tell that for a system undergoing a process the energy required to supply is the energy that the process 'costs' minus the energy you will get automatically from heat flowing into the system?

$$ \text{Energy cost of a process} -\text{Energy supplied 'for free' from the enviroment} = \text{Net Energy needed for a process} $$

So the change of the helmholtz free energy during a process is the net energy needed that you have to supply? Or when it is negative, the energy that is released?

Are there comparable intuitive explanations of the other thermodynamic potentials?

Qmechanic
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bananenheld
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2 Answers2

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I believe it's useful to remember the first law of thermodynamics, $dE = dQ + dW$, which tells us that heat Q and work W are both forms of energy (you can increase the internal energy E of you hands by either rubbing them or place them near a source of heat). Energy conservation is its interpretation; if heat $dQ > 0$ is supplied to the system then the maximum amount of work the system would do on the environment is $dW = dE - dQ$ (where, for work done on the environment by the system, dW is negative).

If 'reversibility is assumed (i.e., if there's no friction, and if the heat transfers are done infinitesimally), then we can say $dW = dE - TdS$, otherwise $dW \ge dE - TdS$. Since $F=E-TS$, then $dF=dE-(TdS+SdT)$, and for isothermal processes we have $dF=dE-TdS$ (since $dT=0$). Hence $dF \le dW$.

If the system was a gas at pressure p, enclosed in a container with volume V connected to a piston, upon heating it would expand; it would do work $dW=-pdV$ on the environment. Hence $dF \le -pdV$, and so $\Delta F \le -\int_a^b p \,dV $, where $b>a$. Negative changes in F indicate work done by the system on the surroundings.

In other words, for systems that are in thermal contact with their surroundings (so that the processes that may occur are isothermal), you can think of $\Delta F$ as the maximum amount of work that you'll be able to get out of the system before equilibrium is reached.

If in addition to being in thermal contact the system is 'mechanically isolated', no work can be applied to or extracted from it, and therefore $dF \le 0$ - meaning that equilibrium is reached when F is minimized and is a constant. An example of such as system could be an idealized spin-$\frac{1}{2}$ paramagnet in the presence of a magnetic field, with non-interacting spins. Since $F=E-TS$, for such a system to reach equilibrium, it will find the right balance between between internal energy E and entropy S at the given temperature T, in order to minimize F. If temperature is low, the system will minimize the internal energy by lining the spins in the direction of the field, even though this would lead to high entropy. If temperature is high, it would randomize the spins to increase its entrope, even though this increases its internal energy.

I hope these examples help you form an intuitive understanding for the Helmholtz function for the cases of systems at constant temperature. Other thermodynamic potentials become relevant for other constraints (e.g., constant pressure, etc) and it's possible to think of intuitive interpretations for them as well. I recommend the book 'Conccepts in Thermal Physics' by Blundell.

Solomon
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  • Can't seem to be able to reply to hft's comment below, however your expression for $dF$ is definitely correct, as long as we assume that the system is in thermal contact with the environment so that the temperature is fixed. – Solomon Jun 16 '22 at 18:19
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What is the interpretation of $dE - TdS \leq 0$?

If I understand correctly this is the Helmholtz free energy: $$ dF = dE - TdS $$

No. The above expression for $dF$ is wrong.

The correct differential is derived as follows:

$$ F = U-TS $$ $$ dF = dU - d(TS) = dU -TdS - SdT \neq dU - TdS $$

Now, using $dU = -pdV - TdS$, we have: $$ dF= dU - TdS - SdT = TdS - pdV - TdS - SdT $$ $$ = -pdV - SdT $$

$F$ is a function of $T$, not of $S$.

hft
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