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    2.2.2. 2nd Law II

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    Palesa Maope
    1) The lecture discusses the molecular interpretation of entropy and how it relates to the probability of different microstates of a system. 2) It introduces the 3rd law of thermodynamics which states that the absolute entropy of a perfectly crystalline substance approaches zero as the absolute temperature approaches zero. 3) Gibbs free energy is discussed as an alternative criterion for spontaneity under constant temperature and pressure conditions, where a spontaneous process is one where the change in Gibbs free energy is negative.

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    2.2.2. 2nd Law II

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    Palesa Maope
    18 views35 pages
    1) The lecture discusses the molecular interpretation of entropy and how it relates to the probability of different microstates of a system. 2) It introduces the 3rd law of thermodynamics which states that the absolute entropy of a perfectly crystalline substance approaches zero as the absolute temperature approaches zero. 3) Gibbs free energy is discussed as an alternative criterion for spontaneity under constant temperature and pressure conditions, where a spontaneous process is one where the change in Gibbs free energy is negative.

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    part two of the second law of thermodynamics

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    1) The lecture discusses the molecular interpretation of entropy and how it relates to the probability of different microstates of a system. 2) It introduces the 3rd law of thermodynamics which states that the absolute entropy of a perfectly crystalline substance approaches zero as the absolute temperature approaches zero. 3) Gibbs free energy is discussed as an alternative criterion for spontaneity under constant temperature and pressure conditions, where a spontaneous process is one where the change in Gibbs free energy is negative.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    18 views35 pages

    2.2.2. 2nd Law II

    Uploaded by

    Palesa Maope
    1) The lecture discusses the molecular interpretation of entropy and how it relates to the probability of different microstates of a system. 2) It introduces the 3rd law of thermodynamics which states that the absolute entropy of a perfectly crystalline substance approaches zero as the absolute temperature approaches zero. 3) Gibbs free energy is discussed as an alternative criterion for spontaneity under constant temperature and pressure conditions, where a spontaneous process is one where the change in Gibbs free energy is negative.

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    Lecture 2.2.2.

    2 LAW OF THERMODYNAMICS II
    nd

    Introduction to a lecture series by


    Physical Chemistry Dr. T.A. Ntho
    Fluid States and Thermodynamics Department of Chemistry
    C2640
    NUL
    Molecular Interpretation of Entropy
    Recall the isolated mixing of 2 ideal gases at constant T and P:

    remove barrier
    Molecular Interpretation of Entropy

    For an isolated system, processes tend to proceed in


    directions that maximize its probability up until a state
    with maximum probability, the equilibrium state.
    Molecular Interpretation of Entropy
    Relating probability (Ω) and entropy (S): S=S(Ω)

    S1, Ω1

    S2, Ω2
    Molecular Interpretation of Entropy
    • Ludwig Boltzmann definition of entropy:

    # of microstates: ways of
    distributing the particles in the
    Boltzmann’s constant:
    system
    1.38 x 10-23 J/K
    Molecular Interpretation of Entropy

    For an isolated system, energy is conserved


    and it is the distribution of energy, which is
    related to entropy, that determines direction
    of spontaneity
    Entropy and Microstates
    • Implications of molecular interpretation of entropy

    -q
    system
    The 3rd Law of Thermodynamics
    absolute entropy approaches zero as the
    absolute temperature approaches zero

    For a perfectly crystalline material

    ABSOLUTE ZERO: lowest possible temperature.


    Significance of the 3rd Law

    S=0
    (at T=0 K)
    Standard Molar Entropies

    Chemistry: The Central Science 12th ed., Brown & LeMay


    Standard Molar Entropies
    Calculating S°
    Standard Molar Entropies
    6
    Cp

    5
    4

    3
    2

    0K Td Tm Tb Temp (K)
    Standard Molar Entropies
    Standard Molar Entropies

    Chemistry: The Central Science 12th ed., Brown & LeMay


    Calculating ∆S°rxn
    Application of Hess’s Law:
    ∆𝑆 ° 𝑟𝑥𝑛 = ෍ 𝑛𝑆 ° 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ෍ 𝑛𝑆 ° 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
    Calculating ∆S°rxn
    Variation with Temperature
    ∆𝑆 ° 𝑟𝑥𝑛 = ෍ 𝑛𝑆 ° 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ෍ 𝑛𝑆 ° 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
    Calculating ∆S°rxn
    Problem 2.2.7. Calculate the molar entropy of formation of NH3(g) at 1000 K given the following:
    𝐽
    𝑚𝑜𝑙 · 𝐾
    𝐽
    𝑚𝑜𝑙 · 𝐾

    𝐽
    𝑚𝑜𝑙 · 𝐾
    Calculating ∆S°rxn
    Problem 2.2.7. Calculate the molar entropy of formation of NH3(g) at 1000 K given the following:
    𝐽
    𝑚𝑜𝑙 · 𝐾
    𝐽
    𝑚𝑜𝑙 · 𝐾

    𝐽
    𝑚𝑜𝑙 · 𝐾
    Calculating ∆S°rxn
    Problem 2.2.7. Calculate the molar entropy of formation of NH3(g) at 1000 K given the following:
    Criteria for Spontaneity
    • For isolated systems:

    𝑑𝑆𝑠𝑦𝑠 ≥ 0

    𝑑𝑆 𝑠𝑦𝑠 > 0: 𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒, 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠 𝑝𝑟𝑜𝑐𝑒𝑠𝑠


    𝑑𝑆 𝑠𝑦𝑠 = 0: 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒, 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
    𝑑𝑆 𝑠𝑦𝑠 < 0: 𝑛𝑜𝑛 − 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠
    Criteria for Spontaneity
    • For non-isolated systems:

    𝑑𝑆𝑢𝑛𝑖𝑣 = 𝑑𝑆𝑠𝑦𝑠 + 𝑑𝑆𝑠𝑢𝑟𝑟 ≥ 0

    𝑑𝑆 𝑢𝑛𝑖𝑣 > 0: 𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒, 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠 𝑝𝑟𝑜𝑐𝑒𝑠𝑠


    𝑑𝑆 𝑢𝑛𝑖𝑣 = 0: 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒, 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
    𝑑𝑆 𝑢𝑛𝑖𝑣 < 0: 𝑛𝑜𝑛 − 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠
    Criteria for Spontaneity

    GOAL: express 2nd Law in terms of other system


    state functions to find an alternative citeria for
    spontaneity at convenient conditions
    Criteria for Spontaneity
    Entropy:
    Criteria for Spontaneity
    Generalized Criteria for Spontaneity: The Clausius Inequality
    Criteria for Spontaneity
    Criteria for Spontaneity
    Consider Enthalpy:
    Criteria for Spontaneity
    Look at more convenient conditions: Constant T and V
    Criteria for Spontaneity
    Look at more convenient conditions: Constant T and P
    Criteria for Spontaneity and Equilibrium
    constant T, constant
    V T, P
    SPONTANEOUS

    EQUILIBRIUM

    NON-SPONTANEOUS

    equilibrium Nature proceeds


    SPONTANEOUSLY to
    a state of
    Suniv A or equilibrium
    G

    equilibrium
    Physical Significance of G and A
    • Helmholtz Energy (A)
    Physical Significance of G and A
    • Gibbs Free Energy (G)
    Physical Significance of G and A
    Helmholtz Energy (A) Gibbs Free Energy (G)
    Maximum work Maximum non-PV work

    Isothermal conditions: Isothermal conditions:

    TdS term represents energy/enthalpy tied up in


    random molecular energy states (HEAT), and is
    therefore unavailable to perform work!
    Calculations of Gibbs Free Energy
    Calculations of Gibbs Free Energy
    Calculation of ∆G°rxn: Application of Hess’s Law

    ∆𝐺 ° 𝑟𝑥𝑛 = ෍ 𝑛∆𝐺 °𝑓,𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ෍ 𝑛∆𝐺 °𝑓,𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠


    Summay of Thermodynamics Discussion

    • 1st Law of Thermodynamics


    • 2nd Law of Thermodynamics
    • 3rd Law of Thermodynamics
    • Alternative criteria for spontaneity
    – Gibbs free energy

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