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Lecture 09 - Chapter 3 - Entropy

1) The second law of thermodynamics states that the entropy of an isolated system always increases and that it is impossible for heat to flow from a cooler body to a hotter body without any work being done. 2) Entropy (S) is a measure of the dispersal of energy and tracks the direction of spontaneous change among permissible changes according to the first law of thermodynamics. 3) The thermodynamic definition of entropy is the heat transferred in a reversible process (dqrev) divided by the temperature (T), and entropy is a state function that is independent of the path between initial and final states.

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44 views

Lecture 09 - Chapter 3 - Entropy

1) The second law of thermodynamics states that the entropy of an isolated system always increases and that it is impossible for heat to flow from a cooler body to a hotter body without any work being done. 2) Entropy (S) is a measure of the dispersal of energy and tracks the direction of spontaneous change among permissible changes according to the first law of thermodynamics. 3) The thermodynamic definition of entropy is the heat transferred in a reversible process (dqrev) divided by the temperature (T), and entropy is a state function that is independent of the path between initial and final states.

Uploaded by

Hyeon Chang No
Copyright
© © All Rights Reserved
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Download as PDF, TXT or read online on Scribd
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Chapter 3

Atkins & de Paula:


Atkins’ Physical Chemistry

Part I: Equilibrium
Chapter 3: The Second Law

Second Law

Spontaneous process:
A process that does not require work to be done to
bring it about

Second law of thermodynamics


(Kelvin statement)
No process is possible in which
the sole result is the absorption
of heat from a reservoir and its
complete conversion into work
3.1 Dispersal of Energy
Bouncing ball:
Energy is spread out as thermal
motion of the atoms of the floor

Direction of change that leads


to dispersal of the total energy
of the isolated system

3.2 Entropy

First Law:
Internal energy (U) is used to identify permissible change
Second Law:
Entropy (S) is used to identify the spontaneous change
among those permissible changes

Second law of thermodynamics (Entropy statement)


The entropy of an isolated system increases in the course of a
spontaneous change: ∆ Stot > 0
Thermo. Definition of Entropy

Thermodynamic definition of Entropy


dq f dqrev Unit of entropy: J K-1
dS = rev ∆S = ∫
T i T Molar entropy: J K-1mole-1
<Example 3.1>
Calculate the entropy change of a sample of perfect gas when it
expands isothermally from a volume Vi to a volume Vf.
dqrev 1 f
f q
∆S = ∫ = ∫ dqrev = rev
i T T i T
∆U = 0 Q Isothermal process
Vf Vf
∴ qrev = − wrev = nRT ln ∴ ∆S = nR ln
Vi Vi

Surrounding Entropy

Entropy of surroundings
dq dq qsur
dS sur = sur ,rev = sur ∆S sur =
Tsur Tsur Tsur

For an adiabatic change : ∆S sur = 0

<Illustration 3.1>
The entropy change in the surroundings when 1 mole of H20 (ℓ)
is formed from its elements under standard conditions at 298K.
Molecular Interpretation

Boltzmann distribution
Ni e − Ei / kT
=
N ∑ e − Ei / kT
i

Statistical entropy (Boltzmann formula)

S = k ln W or S = k ln Ω
where W or Ω : number of microstates
k = 1.381 × 10-23 J K-1
R = NA k

Entropy as a State Function

The entropy as a state function


dS is independent of path
dqrev
∫ T =0

Carnot Cycle:
A cycle composed of alternating isothermal and
adiabatic “reversible” expansions and compressions

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