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Turning inexact heat transfer differential into an exact one

Physics Asked on December 29, 2020

Consider the first law of thermodynamics,

$$ dU = dq +dw$$

simplfying,

$$ dU + P_{text{ext}} dV = dq$$

Now we can say that $ q $ is a function of $ U$ and $V$

$ dq(U,V) = dU + P_{text{ext}} dV$


For a differential $dF(x,y) = A, dx + B, dy $ to be exact,

$$ frac{partial A}{partial y} = frac{partial B}{partial x}$$ is a necessary condition.


Clearly the function $q(U,V)$ doesn’t obey this definition, and hence, let us multiply both sides by an integrating factor $ phi(U,V)$ such that the condition of exact differential is satisfied.

$$ phi(U,V) , dq = phi(U,V) , dU + phi(U,V) P_{text{ext}} , dV$$

For this to be exact,

$$ frac{ partial phi(U,V) P_{text{ext}} }{partial U} = frac{partial phi(U,V) }{partial V}$$

Which leads to:

$$ left( frac{partial P_{text{ext}} }{ partial U} right)_V phi + P_{text{ext}}(frac{partial phi}{partial U})_V =(frac{partial phi}{partial V})_U $$

Now, I’m not sure how to get a general solution for the above partial differential equation…


My real goal is to derive the expression for entropy at end and prove that $ frac{1}{T}$ is the integrating factor but I’m a bit stuck. I’ve seen the proof that $ frac{1}{T}$ is the integrating factor by people pointing to carnots theorem that the circulation of the differentials over a loop is zero but I wanted to derive it using differential equations.

Now, I’m thinking of how I can include the assumption that the process is reversible because the entropy definition is written used $ dq_{text{rev}}$; also maybe derive the entropy generation term.

Any hints?


Reference for integrating factors

One Answer

The choise of the extensive quantities $(U,V)$ as state variables is appropriate, but of course $Q$ is not a state function. It is better to start from the equation of a reversible adiabatic transformation:

$$ dU + p(U,V) dV = 0 $$

If $p(U, V)$ is a known state function of the thermodynamic system the differential equation is integrable and the integration can be carried out with the method of the integrating factor $F(U,V)$:

$$ {{dU + p(U,V)dV} over {F(U,V)}} = dS(U,V) qquad {where:} quad {partial{}over partial{V}} left({1}over{F}right) = {partial{}overpartial{U}} left({p}over{F}right) $$

The differential calculus asserts that integrating factors can always be found and therefore the equation of a reversible adiabatic transformation can be written in the form:

$$ S(U,V) = const $$

where S is a state function such that:

$$ {partial{S}overpartial{U}} = {{1}over{F}} qquad {partial{S}overpartial{V}}={{p}over{F}} $$

Now stop with math! Physical arguments allow to prove that exists an universal integrating factor (independent of the particular system considered!) called absolute thermodynamic temperature $T$ and that this factor is directly proportional to the absolute temperature defined by the gas thermometer.

For this discussion I must refer to the section 6 of an italian link (unfortunately I haven't had time to translate the pdf into English so far):

http://pangloss.ilbello.com/Fisica/Termodinamica/lavoro_calore.pdf

In this way the goal of defining entropy by differential means is achieved:

$$ dS(U,V) = {{dU + p(U,V)dV}over{T}} = {dQ over T} $$

Correct answer by Pangloss on December 29, 2020

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