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    article that could possible break the back bone of thermodynamics second law, invalidity oon thermodynamic irreversibility of an adiabatic process

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    A Critique On Caratheodory Principle of The Second

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    A Critique on Caratheodory Principle of the Second Law of Thermodynamics

    Article · March 2011


    Source: arXiv

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    Radhakrishnamurty Padyala
    Central Electrochemical Research Institute
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    1

    A Critique on Caratheodory Principle of the Second Law of


    Thermodynamics
    P. Radhakrishnamurty
    42, Shivakrupa 1st Floor, 3A Main, Manjunathanagar, 2nd Phase
    Bangalore – 560010, India. e-mail:[email protected]

    Abstract

    Caratheodory’s axiomatic formulation of the second law is considered as one of the standard
    forms of formulation of the law. However, it was mired in advanced mathematics. The formulation was
    strongly criticized by Max Planck, for it was based on the analysis of adiabatic processes and adiabatic
    accessibility. A thermodynamic process is said to be possible only if it satisfies both first law and the
    second law. A process is said to violate the second law only when it satisfies the first law, and violate the
    second law. We show here that violation of Caratheodory principle of the second law violates the first law
    itself. In other words, adiabatic inaccessibility arises only as a consequence of violation of the first law.
    This we demonstrate by assuming, in contradiction to Caratheodory’s principle, that the states considered
    adiabatically inaccessible as adiabatically accessible, and prove that the assumption leads to no paradox –
    thereby showing that the adiabatic inaccessibility arises as a result of violation of the first law.
    __________________________________________________________________________________

    Introduction
    Caratheodory Principle of Second Law of Thermodynamics is rated as one amongst the
    most standard forms of the statement of the law. Till the beginning of the last century, the
    development of this law was considered to be lacking mathematical rigor [1]. The
    required rigor was supplied by the mathematician, Caratheodory, at the instance of Max
    Born, in 1909. His formulation of the second law was axiomatic and highly
    mathematical. Even so, many works follow Caratheodory line of approach. This is more
    so the case with the more mathematically inclined ones. However, it is not as popular as
    the second law formulations of Kelvin and Clausius. It was better understood only after
    Born explained the formulation in clearer terms. The development of Caratheodory’s
    axiomatic thermodynamics is presented recently by L. Pogliani and M. N. Berbaran-
    Santos [2].

    Thermodynamics predicts whether a given process under given conditions is or is not


    possible. Thermodynamics declares a process to be impossible, if it violates either the
    first law or the second law or both. Therefore, for a process to be possible in
    thermodynamics sense it must satisfy both the first and the second law. Processes that
    satisfy the first law need not necessarily satisfy the second law; but the converse is not
    true. All the processes that satisfy the second law must necessarily satisfy the first law.

    A process is said to violate the second law, only if it satisfies the first law and violates the
    second law. Therefore, a valid statement of the second law must satisfy the basic
    requirement that the processes it addresses must satisfy the first law of thermodynamics.

    We demonstrate in this note that, violation of Caratheodory principle of second law of


    thermodynamics implies violation of the first law itself. Consequently, Caratheodory
    principle cannot be considered as a statement of the second law of thermodynamics.
    2

    Caratheodory’s principle of the second law


    Caratheodory Principle of Second Law of Thermodynamics states: “In every arbitrarily
    close neighborhood of a given initial state there exist states that cannot be approached
    arbitrarily closely by adiabatic processes” [3].

    Caratheodory Principle of the First Law of Thermodynamics [3], as applicable to an


    adiabatic process undergone by a closed system, is given by the expression:

    ∆U = W (1)

    Where U is the internal energy of the system (forces acting at a distance and those of
    capillary action are assumed to be absent and not included in the forces of interaction
    between the system and surroundings), ∆U is the change in U suffered by the system due
    to the process undergone by the system. W is the energy in the form of mechanical work
    interaction between the system and the surroundings due to the said process .

    By definition, a closed system undergoing an adiabatic process can neither exchange


    matter nor heat with the surroundings. Therefore, in an adiabatic process a system can
    exchange energy only in the form of work interactions with the surroundings.

    Adiabatic inaccessibility arises due to violation of first law


    Let us consider any two arbitrarily close neighboring equilibrium states of a closed
    system A, B that satisfy the Caratheodory requirements [3]. Then, one of these two states,
    say B, is not accessible from the other state A, by an adiabatic process. But State A is
    accessible from state B by an adiabatic process. Let UA and UB represent the
    corresponding internal energies of the system in the two states.

    We now assume, in contradiction to the Caratheodory principle of the second law, that
    the two chosen equilibrium states are approachable from each other by an adiabatic
    process. This assumption assures us a cyclic adiabatic process. We then demonstrate that
    this assumption leads to results that satisfy the first and second laws of thermodynamics.
    More specifically the assumption does not lead to a violation of the second law.
    Therefore, Caratheodory’s adiabatic inaccessibility must arise only as a result of a
    violation of the first law. This is because impossibility of adiabatic cyclic processes can
    arise only as a result of violation of the first law of thermodynamics.

    Let the system undergo an adiabatic process from one equilibrium state to another
    equilibrium state, say from A to B. Let the energy of work interaction for the process be
    W units. Noting that U is a state function, the first law demands,

    We note that the statement of the first law of thermodynamics as applicable to an arbitrary process of a
    closed system includes one more term, Q, on RHS of eq (1). Q is the energy in the form of heat interaction
    the system suffers due to the process. Thus, the first law as applicable to an arbitrary process of a closed
    system is expressed as: ∆U = W + Q.
    3

    (UB –UA) = ∆U = W (2)

    State B is not reachable by an adiabatic process from state A, only if ∆U ≠ W (note that
    neither the system nor the surroundings suffer entropy change for the adiabatic cycle
    ABA). In other words state B is not reachable from state A by an adiabatic process only if
    the first law is violated. Thus, our demonstration is complete in this case.

    Interlude: An elaboration is in order, here. When a process satisfies the first law it
    implies that the process is possible in both forward and reverse directions. The second
    law however, restricts that possibility only for certain processes – the so called reversible
    processes. For irreversible processes, the second law denies the possibility of occurrence
    of a process in a certain direction. For example, the second law denies the direction of
    the process of conversion of energy in the form of heat to energy in the form of work in a
    one-temperature (1-T) cyclic process; but not the process per se, for, it allows the
    possibility of the process in the opposite direction - the direction of conversion of energy
    in the form of work to energy in the form of heat in a 1-T cyclic process. As a second
    example, we may consider transfer of energy in the form of heat from a body at a given
    temperature to another body at a lower temperature. Second law denies the possibility of
    occurrence of this process in the reverse direction.

    The crux of the second law lies in the fact that it helps us to predict the direction in which
    a process that satisfies the first law occurs under given conditions. It is the first law that
    denies the process per se – when the process corresponds to perpetual motion of the first
    kind – a process that produces energy as output with no input energy or more output
    energy than the input energy. To conclude, the first law can deny the possibility of a
    thermodynamic process, the second law can only deny the possibility of a cyclic process
    in a certain direction. If a process AB is impossible, then the cycle ABA that takes the
    system back to its original state, either in clockwise direction or anticlockwise direction,
    becomes impossible. The second law is incapable of denying the occurrence of a cyclic
    process that satisfies the first law, both in clockwise and anticlockwise directions.
    Consequently, adiabatic inaccessibility is a consequence of violation of the first law.
    (End of interlude).

    We now consider the adiabatic process from state B to state A that brings the system back
    to its original state. The work interaction W for this process is such that

    (UA – UB) = -∆U = -W (3)

    If, -∆U ≠ -W, the first law is violated and our demonstration is complete.

    For the complete cycle, ABA (or BAB),

    W - W = ∆U - ∆U = 0 (4)

    Therefore, arbitrarily chosen neighboring equilibrium states A and B of a system can


    always be connected by an adiabatic process, if the process does not violate the first law.
    4

    The impossibility of approachability of an arbitrarily close equilibrium state in the


    neighborhood of a given equilibrium state of a system by an adiabatic process in
    Caratheodory principle, therefore, can arise only if, ∆U ≠ W for that adiabatic process.
    The impossibility of the said process thus implies the violation of the first law of
    thermodynamics itself. This completes our demonstration.

    References
    [1] Joseph Kestin, The second law of thermodynamics: Benchmark papers on
    energy, Vol. 5, DH&R, Pennsylvania (1976), page 206.
    [2] Lionello Pogliani and Mario N Berberan-Santos, J. Math. Chem. 26, 313-324
    (2000).
    [3] C. Caratheodory, The Second Law of Thermodynamics, Benchmark Papers on
    Energy / 5, Edited by Joseph Kestin, DH&R Inc., Stroudsburg, This article was
    translated expressly for the Benchmark Volume by J Kestin, Brown Univ. from
    “untersuchungen uber die Grundlagen der Thermodynamik,” in Math. Ann.
    (Berlin), 67, 355-386 (1909).

    Acknowledgement
    I wish to express my sincere thanks to Karel Netocny of the Institute of Physics AS CR,
    Prague for useful comments on an earlier version of this article.

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