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    The Second Law: 《 《 《 《 Physical Chemistry, 8th Edition 》 》 》 》

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    febiola silvia ningsih
    This chapter discusses the second law of thermodynamics and entropy. Section 3.1 introduces the concept of entropy and how it relates to the dispersal of energy. Section 3.2 defines entropy more formally and discusses how it applies to spontaneous processes and temperature scales. The chapter then examines how the first and second laws combine to form fundamental equations for thermodynamic properties like the Helmholtz and Gibbs energies.

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    The Second Law: 《 《 《 《 Physical Chemistry, 8th Edition 》 》 》 》

    Uploaded by

    febiola silvia ningsih
    170 views20 pages
    This chapter discusses the second law of thermodynamics and entropy. Section 3.1 introduces the concept of entropy and how it relates to the dispersal of energy. Section 3.2 defines entropy more formally and discusses how it applies to spontaneous processes and temperature scales. The chapter then examines how the first and second laws combine to form fundamental equations for thermodynamic properties like the Helmholtz and Gibbs energies.

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    Atkins Chapter03.Lect01

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    This chapter discusses the second law of thermodynamics and entropy. Section 3.1 introduces the concept of entropy and how it relates to the dispersal of energy. Section 3.2 defines entropy more formally and discusses how it applies to spontaneous processes and temperature scales. The chapter then examines how the first and second laws combine to form fundamental equations for thermodynamic properties like the Helmholtz and Gibbs energies.

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    © All Rights Reserved
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    Download as pdf or txt
    170 views20 pages

    The Second Law: 《 《 《 《 Physical Chemistry, 8th Edition 》 》 》 》

    Uploaded by

    febiola silvia ningsih
    This chapter discusses the second law of thermodynamics and entropy. Section 3.1 introduces the concept of entropy and how it relates to the dispersal of energy. Section 3.2 defines entropy more formally and discusses how it applies to spontaneous processes and temperature scales. The chapter then examines how the first and second laws combine to form fundamental equations for thermodynamic properties like the Helmholtz and Gibbs energies.

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    © All Rights Reserved
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    of 20

    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

    P.76
    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

    P.76
    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)

    Chapter 3. The Second Law P.78


    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

    Chapter 3. The Second Law P.81


    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.
    Chapter 3. The Second Law P.82
    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
    Chapter 3. The Second Law P.84
    Chapter 3. The Second Law P.84
    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

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