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    1) The fundamental postulate of statistical thermodynamics states that the observed energy of a system corresponds to the average energy over all possible states of the ensemble, with each state weighted by its probability. 2) The internal energy (E) of a system can be calculated from the partition function (Q) using the relation E = (∂lnQ/∂β)N,V. 3) For a monatomic ideal gas, the partition function can be written in terms of the single particle partition function (q), which allows calculation of the internal energy and demonstrates that it agrees with the classical kinetic theory result.

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    1) The fundamental postulate of statistical thermodynamics states that the observed energy of a system corresponds to the average energy over all possible states of the ensemble, with each state weighted by its probability. 2) The internal energy (E) of a system can be calculated from the partition function (Q) using the relation E = (∂lnQ/∂β)N,V. 3) For a monatomic ideal gas, the partition function can be written in terms of the single particle partition function (q), which allows calculation of the internal energy and demonstrates that it agrees with the classical kinetic theory result.

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    16 views7 pages

    Statistical Molecular Thermodynamics: Christopher J. Cramer

    Uploaded by

    adiaz
    1) The fundamental postulate of statistical thermodynamics states that the observed energy of a system corresponds to the average energy over all possible states of the ensemble, with each state weighted by its probability. 2) The internal energy (E) of a system can be calculated from the partition function (Q) using the relation E = (∂lnQ/∂β)N,V. 3) For a monatomic ideal gas, the partition function can be written in terms of the single particle partition function (q), which allows calculation of the internal energy and demonstrates that it agrees with the classical kinetic theory result.

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    © All Rights Reserved
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    of 7

    Statistical Molecular

    Thermodynamics
    Christopher J. Cramer
    Video 3.3
    Ideal Gas Internal Energy

    Fundamental Postulate of
    Statistical Thermodynamics
    The observed energy of a given system corresponds to the
    average energy over all possible states of the ensemble each
    weighted according to its respective probability

    "#E j (N ,V )

    E j (N,V )e
    E = $ pjE j = $
    Q(N,V,#)
    j
    j

    Relation of E and Q
    Q( N,V,") = $ e
    j

    #"E j ( N ,V )

    "#E j (N ,V )

    E j (N,V )e
    E =$
    Q(N,V,#)
    j

    Some elementary differential calculus:

    "lnQ 1
    =
    "Q
    Q

    $ "Q '
    *#E j ( N ,V )
    =
    *
    E
    N,V
    e
    (
    )
    & ) ! + j
    % "# ( N ,V
    j

    So,

    % #lnQ!(
    % #lnQ (% #Q (
    1
    "$E j ( N ,V )
    "'
    =
    "
    =
    E
    N,V
    e
    = E
    (
    )
    '
    *' *
    +
    *
    j
    & #Q )& #$ ) N ,V Q j
    & #$ ) N ,V

    Relation of E and Q
    Q( N,V,") = $
    j

    "#E j (N ,V )

    E j (N,V )e
    e
    E =$
    Q(N,V,#)
    j
    % #lnQ (
    E = "'
    *
    & #$ ) N ,V
    #"E j ( N ,V )

    Or, if more convenient to !


    work with T instead of

    1
    "=
    kBT

    ! 1 $
    ! ! lnQ $ ! !" $
    ! ! lnQ $
    #
    & =#
    & # & = (' E ) # '
    !
    2&
    " ! T %N,V " !" %N,V " ! T %N,V
    " kBT %

    which rearranges to:


    # "lnQ &
    E = kBT %
    (
    $ "T ' N ,V
    2

    Practical Utility of Q
    We have proven that statistical thermodynamics permits
    calculation of macroscopic (thermodynamic) properties
    (e.g., energy) for a large collection of particles (e.g.,
    molecules) from the partition function Q. But, how do we
    get the partition function? A brobdingnagian task
    The simplest example: a monatomic ideal
    gas (e.g., He). In that case, Q can be written as:

    q(V,")]
    [
    Q(N,V,") =
    N!

    q: partition function for 1 atom



    m: mass of atom
    h: Plancks constant

    $ 2#m ' 2
    q(V,") = & 2 ) V
    % h "(

    Derivations soon

    Some Calculus
    Given:
    Then,

    !
    And,

    q(V,")]
    [
    Q(N,V,") =
    N!

    $ 2#m ' 2
    q(V,") = & 2 ) V
    % h "(

    lnQ = N lnq " ln N!


    ! 2
    3
    = N (ln2#m " ln h " ln$) + N lnV " ln N!
    2

    % #lnQ (
    3 "1 3
    "'
    * = N$ = NkBT = E
    2
    & #$ ) N ,V 2
    pretty simple!

    Monatomic Ideal Gas Redux


    From the kinetic theory of
    gases and from experiment,
    we know that the molar
    internal energy (U) of a
    monoatomic ideal gas is:

    % # lnQ (
    E = "'
    *
    & #$ ) N ,V

    U = 32 RT

    3
    2

    E = NkBT
    This result demonstrates the power of statistical
    thermodynamics. From microscopic properties,
    we can calculate a macroscopic quantity that can
    be measured. It also establishes that Boltzmanns
    constant is equal to the universal gas constant R
    divided by Avogadros number NA

    molar quantity
    (i.e., per mole)

    U= E

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