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Chemistry LibreTexts

19.4: An Adiabatic Process is a Process in which No Energy as Heat is Transferred

Isothermal expansion of an ideal gas

For a monatomic ideal gas we have seen that energy \(\langle E \rangle\) observed as \(U= 3/2 nRT\). This means that energy is only dependent on temperature and if a gas is compressed isothermally, then the internal energy does not change:

\[ΔU_{isothermal-ideal gas} = 0\]

This means that the reversible work must cancel the reversible heat:

\[ΔU_{rev} = w_{rev} + q_{rev} = 0 \]

Therefore

\[w_{rev} = - q_{rev}\]

so from the expression of the reversible work for expansion in the last section

\[ q_{rev}= nRT\ln \dfrac{V_2}{V_1}\]

If \(V_2>V_1\) (expansion), then you (or the environment) must put heat into the system because this is a positive number.

Adiabatic expansion of an ideal gas

Now suppose you make sure that no heat can enter the cylinder. (Put it in styrofoam or so). Then the path can still be reversible (slow pulling) but the process is then adiabatic

This bat- part comes from a Greek verb βαινω (baino) that means walking, compare acrobat, someone who goes high places (acro-). The δια (dia) part means 'through' (cf. diagram, diorama, diagonal etc.) and the prefix α- (a-) denies it all (compare atypical versus typical).

So the styrofoam prevents the heat from walking through the wall. When expanding the gas from V1 to V2 it still does reversible work but where does that come from? It can only come from the internal energy itself. So in this case any energy change should consist of work (adiabatic means: \(δq=0\)).

\[dU = δw_{rev}\]

This implies that the temperature must drop, because if \(U\) changes, then \(T\) must change.

The change of energy with temperature at constant volume is known as the heat capacity (at constant volume) \(C_v\)

\[ C_v =\left( \dfrac{\partial U}{\partial T} \right)_V\]

For an ideal gas \(U\) only changes with temperature, so that

Image:CH431_Image61.gif

or:

Image:CH431_Image62.gif

We can now compare two paths to go from state 1 to state 2

  1. isothermal reversible expansion A
  2. adiabatic reversible expansion B followed by isochoric (V=constant) heating C
Image:CH431_adiabat.jpg

Notice that the temperature remains T1 for path A (isotherm!), but that it drops to T2 on the adiabat (B), so that the cylinder has to be warmed up (C) to regain the same temperature.

ΔUtot should be the same for both A and (B+C), because the end points are the same (U is a state function!). As the and points are at the same temperature and U only depends on T ΔUtot = 0

Along the adiabat B

\[q_{rev}=0.\]

Along the heating path C, there is no volume work because the volume is kept constant, so that.

Image:CH431_Image63.gif

This is the only reversible heat involved in path B+C.

However, we know that ΔUtot for path A is zero (isothermal!). This means that the volume work along B must cancel the heat along C:

The book keeping looks as follows, all paths are reversible:

ΔUB+C = ΔUA = 0 = qB + wB + qC + wC (A is isothermal path: T=const, U=constant)
ΔUB+C = ΔUA = 0 = 0 + wB + qC + wC (B is adiabatic q=0)
ΔUB+C = ΔUA = 0 = 0 + wB + qC + 0 (C is isochoric, V=constant => w=0)
So: wB = - qC

We had already seen before that along the isotherm A

\[w_A = - q_A = - nRT \ln \dfrac{V_1}{V_2}\]

As you can see wA and wB are not the same thing. (WORK IS A PATH FUNCTION even if reversible). As we are working with an ideal gas we can be more precise about \(w_B\) and \(q_c\) as well. The term \(w_B\) along the adiabat is reversible volume work. Since there is no heat along B we can write a straight d instead of ∂ for the work contributions (It is the only contribution and must be identical to the state function dU):

Image:CH431_Image64.gif