Temperature Dependence of Latent Heat for an Ideal Gas

We derive the liquid-gas phase boundary with the Clausius-Clapeyron equation, then dig into why latent heat L actually depends on temperature.

Example 28.2

Derive the equation for the phase boundary between liquid and gas, under the assumptions that the latent heat L is independent of temperature, the vapor is treated as an ideal gas, and V_vapour = V » V_liquid.

Let me solve this problem.

As I previewed earlier, I’ll solve the problem with the Clausius-Clapeyron equation.

The equation whose focus is ’the very moment a phase transition happens’ was the Clausius-Clapeyron equation,

and therefore the C-C equation can be understood as an equation about ‘phase transitions’.

Equation from the original notes

If we apply the ideal gas to this equation — since this is the equation for the phase boundary between the liquid and gas of an ideal gas —

applying the ideal gas equation (for 1 mol) pV = RT to the above equation,

Equation from the original notes

But if we apply the ideal gas to this again,

Equation from the original notes

So then this would be the equation for the phase boundary.

(Of course, an ideal gas won’t undergo phase transitions, though.)

Equation from the original notes

*****But, I had understood L as some ‘property’ that didn’t depend on anything,

but actually, L is said to be a physical quantity that depends on temperature.

Let’s have a look.

To figure out how L depends on temperature, what do we do!!!

Apparently there’s a sort of recipe.

Rather than just thinking of L as L(T)

and differentiating with respect to T, we’ll use L(T)/T!!!!!!! And through that we’ll look at L’s temperature dependence. (Like entropy?!)

So if we simply differentiate L(T)/T,

Equation from the original notes

But, we can also pull out an equation like this.

We use L = TΔS.

In this case, it would be L = T(S_vapour - S_liquid).

Then get a feel that L/T can equivalently be expressed as ΔS,

and we separate the change of L/T into a term from p and a term from T.

Equation from the original notes

Now that we’ve written it like this, let’s get into the shenanigans.

Equation from the original notes

What we need to find is

Equation from the original notes

this, so

Equation from the original notes

Organizing it like this,

for the red part we’ll use TdS = dQ,

and the blue part we’ll organize using Maxwell’s relations.

Equation from the original notes

Equation from the original notes

Equation from the original notes

Equation from the original notes

For the red part we’re going to apply the ideal gas equation of state,

first, dV/dT = R/p,

and for the latter term, we can just apply the Clausius-Clapeyron equation with the ideal gas equation applied that we did waaaay up there~ yup~

Equation from the original notes

Equation from the original notes

Okay okay okay so now

we’ve got two expressions for d/dT(T/L).

Equation from the original notes

Therefore,

Equation from the original notes

So the phase coexistence equation we made earlier with the ideal gas assumption thrown in was

Equation from the original notes

rather than this,

Equation from the original notes

this is the rigorous equation!!!

But the point here was to realize that “actually, the latent heat L depends on temperature!!!!”

However, in the discussions that follow, we’ll keep saying “yeah we know it’s temperature-dependent, but let’s just ignore it for now~~~”

and carry the logic forward that way hhh hehehehe

Alright, bb

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