Physical Chemistry for

Engineers – CE1PCE
Session 2: Classical Entropy
Video 1

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) Calculate the change in entropy that occurs for a variety of

processes.

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Entropy changes of specific processes

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 Expansion

𝑽𝒇
Δ 𝑺 𝑺𝒀𝑺=𝒏𝑹𝒍𝒏
𝑽𝒊

We derived this expression for the entropy change ΔS in a system for a

perfect gas expanding isothermally in the last session.

We said that entropy was a state function, which means that ΔS for a
system is independent of the path between initial and final states.

This means that the equation is valid whether the expansion is reversible or
irreversible.

But what about the total entropy change?

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 Expansion

Total entropy change ΔSTOTAL does depend on whether expansion is

reversible or irreversible, to show this we need to consider ΔSSYSTEM at the
same time as ΔSSURROUNDINGS.

𝒒 𝑺 𝑼𝑹 =− 𝒒 𝑹𝑬𝑽 𝑽𝒇
Δ 𝑺 𝑺 𝑼𝑹=−𝒏𝑹𝒍𝒏
𝑽𝒊

For a reversible process the increase in heat of the surroundings is equal and
opposite to the energy lost as heat by the system.

It follows that ΔSSURROUNDINGS is equal and opposite to ΔSSYSTEM .

For a reversible process the ΔSSYSTEM and ΔSSURROUNDINGS cancel out meaning
that the total entropy change must equal zero.

ΔSTOTAL5= 0.
Expansion

For an irreversible process:

𝒒 𝑺𝑼𝑹
Δ 𝑺 𝑺𝑼𝑹= Δ 𝑼 =𝐪 + 𝐰 𝒘 =− 𝐩𝐝𝐕
𝑻 𝑺𝑼𝑹

Δ 𝑺 𝑺𝑼𝑹=𝟎 Δ 𝑼 =𝐪 Δ 𝑼 =𝟎

𝒒=𝟎
Therefore ΔSSYSTEM and ΔSSURROUNDINGS DON’T cancel out.

Therefore ΔSSYSTEM = ΔSTOTAL= .

ΔSTOTAL> 0

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Phase Transitions

If the system is at its TTRANS

between two phases at
constant p then those
phases are in equilibrium,
which means that any heat
transfer is reversible.

At constant p, q = ΔHTRANS

Δ 𝑯 𝑻𝑹𝑨𝑵𝑺
Δ 𝑺𝑻𝑹𝑨𝑵𝑺 =
𝑻 𝑻𝑹𝑨𝑵𝑺

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 Trouton’s Rule

Many liquids have the same ΔSVAP ≈ 85 J K-1 mol-1.

Observed because many liquids undergo a comparable

volume change upon vaporization and hence a comparable
increase in the number of MICROSTATES.

Liquids that deviate from Trouton’s rule are those that have
significant intermolecular interactions (e.g. H – bonding in
water) which create a much more ordered liquid.

Can use Trouton’s rule to approximate the enthalpy of

vaporization for many liquids.

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Heating
𝒇
𝒅 𝒒 𝒓𝒆𝒗
𝑺 ( 𝑻 𝑭𝑰𝑵𝑨𝑳 )=𝑺 ( 𝑻 𝑰𝑵𝑰𝑻𝑰 𝑨𝑳 ) + Δ 𝑺 𝑺𝒀𝑺𝑻𝑬𝑴 Δ 𝑺 𝑺𝒀𝑺=∫
𝒊 𝑻

𝒇
𝒅 𝒒𝒓𝒆𝒗
𝑺 ( 𝑻 𝑭𝑰𝑵𝑨𝑳 )=𝑺 ( 𝑻 𝑰𝑵𝑰𝑻𝑰 𝑨𝑳 ) +∫ 𝒅𝒒𝒓𝒆𝒗 =𝑪 𝑷 𝒅𝑻
𝒊 𝑻

𝒇
𝑪 𝑷 𝒅𝑻
𝑺 ( 𝑻 𝑭𝑰𝑵𝑨𝑳 )=𝑺 ( 𝑻 𝑰𝑵𝑰𝑻𝑰 𝑨𝑳 ) +∫
𝒊 𝑻

𝒇 But how do we
𝒅𝑻
𝑺 ( 𝑻 𝑭𝑰𝑵𝑨𝑳 )=𝑺 ( 𝑻 𝑰𝑵𝑰𝑻𝑰 𝑨𝑳 ) + 𝑪 𝑷 ∫ get S(TINITIAL)???
𝒊 𝑻

𝑻 𝑭𝑰𝑵𝑨𝑳
𝑺 ( 𝑻 𝑭𝑰𝑵𝑨𝑳 )=𝑺 ( 𝑻 𝑰𝑵𝑰𝑻𝑰 𝑨𝑳 ) + 𝑪 𝑷 𝒍𝒏
𝑻 𝑰𝑵𝑰𝑻𝑰𝑨 𝑳
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