Atkins / Paula

《 Physical Chemistry, 8th Edition 》

Chapter 3.
The Second Law
 The direction of spontaneous change
3.1 The dispersal of energy
3.2 Entropy
3.3 Entropy changes accompanying
specific processes
3.4 The Third Law of thermodynamics

Concentrating on the system

3.5 The Helmholtz and Gibbs energies
3.6 Standard reaction Gibbs energies

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Combining the First and Second Laws
3.7 The fundamental equation
3.8 Properties of the internal energy
3.9 Properties of the Gibbs energy

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 Some aspect of the world
determines the spontaneous
direction of change, the
direction of change that does
not require work to be done
to bring it about.

2nd Law of thermodynamics

(Kelvin)
No process is possible in which
the sole result is the absorption
of heat from a reservoir and its
complete conversion into work.

Chapter 3. The Second Law P.77

 3.1 The dispersal of energy

Chapter 3. The Second Law P.77

 3.1 The dispersal of energy
(cont’d)

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 3.2 Entropy
• 2nd Law of thermodynamics:
• The entropy of an isolated system increases
in the course of a spontaneous change: ∆S
tot > 0
• Stot - total entropy of the system and its
surroundings
• (a) The thermodynamic definition of
entropy
 Ex 3.1 Calculating the entropy change for the isothermal
expansion of a perfect gas
• Calculate the entropy change of a sample of
perfect gas when it expands isothermally from a
volume Vi to a volume Vf.
• Answer At const temperature
•
• From eqn 2.11
•

•
• When the volume occupied by 1.00 mol of any
perfect gas molecules is doubled at any const
temperature, Vf/Vi = 2 and
• Illustration 3.1 Calculating the entropy change in the surroundings
• To calculate the entropy change in the surroundings when 1.00 mol H2O(l) is
formed from its elements under standard conditions at 298 K, use ∆H ° = −286
kJ from Table 2-7. The energy released as heat is supplied to the surroundings,
now regarded as being at constant pressure, so qsur = +286 kJ. Therefore,

• This strongly exothermic reaction results in an increase in the entropy of the

surroundings as energy is released as heat into them.
• Test 3.2 Calculate the entropy change in the surroundings when 1.00 mol
N2O4(g) is formed from 2.00 mol NO2(g) under standard conditions at 298 K.
• Answer: −192 J K−1
3.2 Entropy
Boltzmann distribution:

Boltzmann formula
statistical entropy

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3.2(b) The entropy as a
state function (eqn 3.6)

1. Show that eqn 3.6 is

true for a special cycle
(a ‘Carnot cycle’)
involving a perfect gas.
2. Show that the result
is true whatever the
working substance.
3. The result is true for
any cycle.
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Carnot cycle 1. Reversible isothermal expansion
from A to B at Th; the entropy change
is q h/Th, q h is the energy supplied to
the system as heat from the hot source.
2. Reversible adiabatic expansion
from B to C. No energy leaves the
system as heat, change in entropy is 0.
Temp. falls from Th to Tc, temp. of
cold sink.

Chapter 3. The Second Law P.81

Carnot cycle (cont’d)
• 3. Reversible isothermal
compression from C to D at
Tc. Energy is released as
heat to the cold sink; the
change in entropy of the
system is qc/Tc; in this
expression qc is negative.
• 4. Reversible adiabatic
compression from D to A.
No energy enters the
system as heat, so the
change in entropy is zero.
The temperature rises from
Tc to Th.
 For perfect gas

eqn 3.7:
• Heating accompanying reversible adiabatic expansion
• The two temperatures in eqn 3.7 lie on the same adiabat.
For a perfect gas:
•

• From the relations between temperature and volume for

reversible adiabatic processes (eqn 2.28):
• VAThc = VDTcc VcTcc = VBThc
• Multiplication of the first of these expressions by the
second gives
• VAVcThcTcc = VDVBThcTcc

•
 efficiency, ε (epsilon),
of a heat engine:

Chapter 3. The Second Law P.83

Chapter 3. The Second Law P.84
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 Refrigeration

coefficient of performance

minimum power

Chapter 3. The Second Law P.85

 3.2 Entropy – (c)The thermodynamic
temperature

• (d) The Clausius inequality

• More energy flows as work under
reversible conditions than under
irreversible conditions. i.e., −dwrev ≥ −dw,
or dw − dwrev ≥ 0.

dqrev − dq = dw − dwrev ≥ 0, or dq rev ≥ dq, so dq rev/T ≥ dq/T