Let's, for the sake of argument, agree that the thermodynamic relation for equilibrium in the form of zero change of the Helmholtz potential, is applicable for particles suspended in a liquid,
δF=δE−TδS=0, (1)
where F is the Helmholtz potential, E is the energy, T is the absolute temperature and S is the entropy. Then, the following integral for δE is written
δE=−∫l0Kνδxdx (2)
where K is the force per unit particle, acting only along the x-axis, ν is the number of particles per unit volume, δx is a variation of x, δx being also a function of x. The liquid is bounded by the planes x=0 and x=1 of unit area.
Now, it can be intuitively seen how, because K is a force on a unit particle, that force has to be multiplied by the number of particles residing on a plane perpendicular to the x-axis and that has led to the expression for δE in eq.(2)
Then, the variation of entropy, δS, is defined as
δS=∫l0kν∂δx∂xdx, (3)
where k is Boltzmann's constant.
Now, from eq.(2) and eq.(3), using eq.(1) we get
−∫l0Kνδxdx=T∫l0kν∂δx∂xdx. (4)
or, if the integrands are continuous functions
−Kδx=kT∂δx∂x. (5)
It seems to me that l.h.s of eq.(5) is not equal to its r.h.s. -- on the l.h.s. we have work with negative sign, while on the r.h.s. we have the expression of energy for two degrees of freedom, according to the equipartition theorem, multiplied by a positive non-zero factor. What do you think about this? Am I right or am I missing something?
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