Thermodynamics MOC

Entropy

Entropy is a somewhat obscure quantity relating to the exchange of heat. The change in entropy for a quasistatic process is defined by1

𝑑𝑆=đ𝑄𝑇

Statistical thermodynamics reveals

𝑆=𝑘𝐵𝐻[𝑀]

where 𝐻 is the Shannon entropy expressed in nat for the Distribution of microstates at equilibrium.

Entropy is a quantity which increases during any Irreversible process. For a real process

𝑑𝑆>đ𝑄𝑇

Thermodynamic entropy postulates

In thermodynamics, the following properties are postulated:

  1. The entropy 𝑆 is a well-defined quantity for equilibrium states as a function of the extensive parameters of a system, e.g. 𝑆 =𝑆(𝐸,𝑉,𝐍).
  2. The entropy of a composite system is the sum of the entropies of its subsystems, i.e. entropy is an extensive parameter.
  3. In an infinitesimal quasistatic process the change in entropy is 𝑑𝑆 =đ𝑄/𝑇.
  4. Entropy maximum principle:2 For an isolated system, the entropy can never decrease, moreover if an internal constraint is removed, the final equilibrium state is that which maximizes entropy.

As a thermodynamic potential

Entropy 𝑆(𝐸,𝑉,𝐍) is the naural Thermodynamic potential for a closed thermodynamic system. Applying the ^Quasistatic,

𝑑𝑆=1𝑇𝑑𝐸+𝑝𝑇𝑑𝑉𝑖𝜇𝑖𝑇𝑑𝑁𝑖

whence

𝜕𝑆𝜕𝐸=1𝑇𝜕𝑆𝜕𝑉=𝑝𝑇𝜕𝑆𝜕𝑁𝑖=𝜇𝑖𝑇


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Footnotes

  1. There is an implicit claim that 𝑑𝑆 is an exact differential and hence the quantity 𝑆 is well-defined for an equilibrium state. For example, see Entropy of an ideal gas.

  2. Essentially the Second law of thermodynamics