Physical Chemistry for

Engineers – CE1PCE
Session 1: Classical entropy
Video 3

Dr Stephen David Worrall

s.worrall@aston.ac.uk
Phone: 0121 204 3179
Office: MB 136
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Intended Learning Outcomes

After this lecture you should be able to:

1) Define entropy both qualitatively and mathematically.

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Entropy

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Entropy

The first law of thermodynamics led to the introduction of the internal

energy U, a state function that lets us determine whether a change is
permissible.

The second law of thermodynamics leads us to introduce another

state function, one that let us determine whether a permissible
change is spontaneous.

This state function is entropy S and the second law of

thermodynamics can be expressed in terms of S.

The entropy of an isolated

system increases in the course
of a spontaneous change;
ΔSTOT > 0.
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Thermodynamic definition of entropy

Thermodynamically we define entropy in terms of how it changes dS

as a result of a process, that a change in how energy is dispersed is
dependent upon how much energy is transferred as heat dqrev at a
given temperature T.

𝒅 𝒒 𝒓𝒆𝒗
𝒅𝑺=
𝑻

𝒇
𝒅 𝒒 𝒓𝒆𝒗
Δ 𝑺 𝑺𝒀𝑺=∫
𝒊 𝑻

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Entropy of the system
Calculate the entropy change of a sample of perfect gas when it expands
isothermally from a volume Vi to a volume Vf.
𝒇
𝒅 𝒒 𝒓𝒆𝒗 𝑽𝒇
Δ 𝑺 𝑺𝒀𝑺=∫ Δ 𝑼 =𝐪 + 𝐰 − 𝒘 𝒓𝒆𝒗 =𝒏𝑹𝑻𝒍𝒏
𝒊 𝑻 𝑽𝒊
𝒒=− 𝐰
𝒇
𝟏
Δ 𝑺 𝑺𝒀𝑺= ∫ 𝒅 𝒒 𝒓𝒆𝒗 𝒒 𝒓𝒆𝒗 =− 𝒘 𝒓𝒆𝒗
𝑻 𝒊

𝒒𝒓𝒆𝒗
Δ 𝑺 𝑺𝒀𝑺= Can now use this
formula easily𝑻to
calculate ΔSSYS for a volume change and
𝑽𝒇 see how it complies with the
Δ 𝑺 𝑺𝒀𝑺law
second =𝒏𝑹𝒍𝒏 of
𝑽𝒊
thermodynamics!

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 Entropy of the surroundings
So far we have talked about the total entropy and the entropy of the
system…but what about the entropy of the surroundings?

𝒅 𝒒 𝒓𝒆𝒗
𝒅𝑺=
𝑻
Δ 𝑼 =𝐪 + 𝐰 𝒘 =− 𝐩𝐝𝐕

𝒅 𝒒 𝑺𝑼𝑹,𝒓𝒆𝒗 Δ 𝑼 =𝐪
𝒅 𝑺 𝑺𝑼𝑹 =
𝑻 𝑺𝑼𝑹

𝒅 𝒒 𝑺𝑼𝑹
𝒅 𝑺 𝑺𝑼𝑹 =
𝑻 𝑺𝑼𝑹
Can now use
this formula easily to
𝒒 𝑺𝑼𝑹 calculate ΔSSUR from the heat transferred
Δ 𝑺 𝑺𝑼𝑹=
𝑻 𝑺𝑼𝑹 at a given
temperature.

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Clausius inequality
How can we prove that the thermodynamic definition of enthalpy
satisfies the second law of thermodynamics?

With Dr Evans you have discussed that the maximum amount of

work is achieved in a reversible change.
𝒅𝑼 =𝐝𝐪 + 𝐝𝐰
− 𝒅 𝒘 𝒓𝒆𝒗 ≥ − 𝐝𝐰
𝒅𝑼 =𝒅𝒒 𝒓𝒆𝒗 + 𝒅𝒘 𝒓𝒆𝒗
𝒅𝒘 − 𝒅 𝒘 𝒓𝒆𝒗 ≥ 𝟎
𝒅𝒒+ 𝒅𝒘 =𝒅𝒒𝒓𝒆𝒗 + 𝒅 𝒘 𝒓𝒆𝒗

𝒅𝒒 ≤ 𝒅𝒒𝒓𝒆𝒗
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 Clausius inequality

𝒅 𝒒 𝒓𝒆𝒗
𝒅𝒒 ≤ 𝒅𝒒𝒓𝒆𝒗 𝒅𝑺=
𝑻

𝒅𝒒
𝒅𝑺≥
𝑻
This is the Clausius inequality, and if we now consider an isolated
system, where dq = 0 then:

𝒅𝑺≥ 𝟎
thus saying that:

In an isolated system the entropy cannot decrease as a result of a

spontaneous change.

Which agrees with the second law of thermodynamics!

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