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    Maxwell Relations

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    Raghav Agrawal
    The Maxwell relations are a set of equations in thermodynamics that relate the second derivatives of the thermodynamic potentials, such as internal energy, enthalpy, Helmholtz free energy and Gibbs free energy. The four most common Maxwell relations equate the second derivatives of these potentials with respect to temperature and pressure or volume. Maxwell's relations follow directly from the fact that the order of differentiation of an analytic function of two variables is irrelevant.

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    Maxwell Relations

    Uploaded by

    Raghav Agrawal
    730 views5 pages
    The Maxwell relations are a set of equations in thermodynamics that relate the second derivatives of the thermodynamic potentials, such as internal energy, enthalpy, Helmholtz free energy and Gibbs free energy. The four most common Maxwell relations equate the second derivatives of these potentials with respect to temperature and pressure or volume. Maxwell's relations follow directly from the fact that the order of differentiation of an analytic function of two variables is irrelevant.

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    maxwell's Relation

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    The Maxwell relations are a set of equations in thermodynamics that relate the second derivatives of the thermodynamic potentials, such as internal energy, enthalpy, Helmholtz free energy and Gibbs free energy. The four most common Maxwell relations equate the second derivatives of these potentials with respect to temperature and pressure or volume. Maxwell's relations follow directly from the fact that the order of differentiation of an analytic function of two variables is irrelevant.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    730 views5 pages

    Maxwell Relations

    Uploaded by

    Raghav Agrawal
    The Maxwell relations are a set of equations in thermodynamics that relate the second derivatives of the thermodynamic potentials, such as internal energy, enthalpy, Helmholtz free energy and Gibbs free energy. The four most common Maxwell relations equate the second derivatives of these potentials with respect to temperature and pressure or volume. Maxwell's relations follow directly from the fact that the order of differentiation of an analytic function of two variables is irrelevant.

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    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
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    At a glance
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    Maxwell relations are equations relating the derivatives of thermodynamic potentials which follow from thermodynamics definitions. They connect properties like heat, pressure, volume and temperature.

    Maxwell relations are statements about the equality of second derivatives of thermodynamic potentials. They follow from the fact that order of differentiation does not matter and from thermodynamic definitions.

    Maxwell relations are derived using rules of partial differentiation applied to thermodynamic equations relating potentials, work terms, temperature and other variables. Symmetry of second derivatives is also used.

    Maxwell relations

    Maxwell relations
    Thermodynamics

    The classical Carnot heat engine

    Maxwell's relations are a set of equations in thermodynamics which are derivable from the definitions of the thermodynamic potentials. These relations are named for the nineteenth-century physicist James Clerk Maxwell.

    Equation
    The Maxwell relations are statements of equality among the second derivatives of the thermodynamic potentials. They follow directly from the fact that the order of differentiation of an analytic function of two variables is irrelevant. If is a thermodynamic potential and xi and xj are two different natural variables for that potential, then the Maxwell relation for that potential and those variables is: Maxwell relations (general) where the partial derivatives are taken with all other natural variables held constant. It is seen that for every thermodynamic potential there are n(n 1)/2 possible Maxwell relations where n is the number of natural variables for that potential.

    The four most common Maxwell relations


    The four most common Maxwell relations are the equalities of the second derivatives of each of the four thermodynamic potentials, with respect to their thermal natural variable (temperature T; or entropy S) and their mechanical natural variable (pressure P; or volume V):

    Maxwell's relations (common)

    where the potentials as functions of their natural thermal and mechanical variables are the internal energy U(S, V), Enthalpy H(S, P), Helmholtz free energy A(T, V) and Gibbs free energy G(T, P). The thermodynamic square can be used as a mnemonic to recall and derive these relations.

    Maxwell relations

    Derivation
    Maxwell relations are based on simple partial differentiation rules, in particular the total differential of a function and the symmetry of evaluating second order partial derivatives.
    Derivation Derivation of the Maxwell relations can be deduced from the differential forms of the thermodynamic potentials:

    These equations resemble total differentials of the form

    And indeed, it can be shown for any equation of the form

    that

    Consider, as an example, the equation

    . We can now immediately see that

    Since we also know that for functions with continuous second derivatives, the mixed partial derivatives are identical (Symmetry of second derivatives), that is, that

    we therefore can see that

    and therefore that

    Each of the four Maxwell relationships given above follows similarly from one of the Gibbs equations.

    Extended derivation Combined form first and second law of thermodynamics, (Eq.1) U, S, and V are state functions. Let,

    Maxwell relations Substitute them in Eq.1 and one gets,

    And also written as,

    comparing the coefficient of dx and dy, one gets

    Differentiating above equations by y, x respectively (Eq.2) and (Eq.3) U, S, and V are exact differentials, therefore,

    Subtract eqn(2) and (3) and one gets

    Note: The above is called the general expression for Maxwell's thermodynamical relation. Maxwell's first relation Allow x = S and y = V and one gets

    Maxwell's second relation Allow x = T and y = V and one gets

    Maxwell's third relation Allow x = S and y = P and one gets

    Maxwell's fourth relation

    Maxwell relations Allow x = T and y = P and one gets

    Maxwell's fifth relation Allow x = P and y = V =1 Maxwell's sixth relation Allow x = T and y = S and one gets =1

    General Maxwell relationships


    The above are not the only Maxwell relationships. When other work terms involving other natural variables besides the volume work are considered or when the number of particles is included as a natural variable, other Maxwell relations become apparent. For example, if we have a single-component gas, then the number of particles N is also a natural variable of the above four thermodynamic potentials. The Maxwell relationship for the enthalpy with respect to pressure and particle number would then be:

    where is the chemical potential. In addition, there are other thermodynamic potentials besides the four that are commonly used, and each of these potentials will yield a set of Maxwell relations. Each equation can be re-expressed using the relationship

    which are sometimes also known as Maxwell relations.

    External links
    a partial derivation of Maxwell's relations [1]

    References
    [1] http:/ / theory. ph. man. ac. uk/ ~judith/ stat_therm/ node48. html

    Article Sources and Contributors

    Article Sources and Contributors


    Maxwell relations Source: http://en.wikipedia.org/w/index.php?oldid=569416784 Contributors: Apyule, Charles Matthews, Complexica, DARTH SIDIOUS 2, Dhollm, Dirac66, Edsanville, Eliyak, Entropy, Epolk, F=q(E+v^B), Fibonacci, Giftlite, Gogobera, Headbomb, Hydrogen Iodide, Icairns, Inutilisable, Japanese Searobin, Liuxunchen, Loodog, MMKO, Machina Lucis, MagiMaster, Makeemlighter, Michael Hardy, Nanomage, PAR, PV=nRT, Pmetzger, Richie, RoB, Screamerman18, Stallionz, Thorwald, Towerman86, Vinayakrishnanmb, WeiWuHere, Wranadu2, , 76 anonymous edits

    Image Sources, Licenses and Contributors


    File:Carnot heat engine 2.svg Source: http://en.wikipedia.org/w/index.php?title=File:Carnot_heat_engine_2.svg License: Public Domain Contributors: Eric Gaba (Sting - fr:Sting)

    License
    Creative Commons Attribution-Share Alike 3.0 Unported //creativecommons.org/licenses/by-sa/3.0/

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