Concerning the definitions of the enthalpy, the Helmholtz free energy and the Gibbs free energy of a systemWhy is the Gibbs Free Energy $F-HM$?Gibbs free energy and maximum workHelmholtz Free Energy vs Gibbs Free Energy in Landau TheoryGibbs' free energy and Helmholtz free energyHow could chemical potential be interpreted as the molar Gibbs free energy?Gibbs Free Energy of Two concurring PhasesHelmholtz Free Energy at EquilibriumPhysical Significance of $U$ (Internal Energy ) , $H$ (Enthalpy) , $F$ (Free Energy) and $G$ (Gibbs Free Energy)?Gibbs free energy the 3 equation confusionIs Entropy a monotonically increasing function of Gibbs Free Energy/ Helmholtz free energy/ Enthalpy?

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Concerning the definitions of the enthalpy, the Helmholtz free energy and the Gibbs free energy of a system


Why is the Gibbs Free Energy $F-HM$?Gibbs free energy and maximum workHelmholtz Free Energy vs Gibbs Free Energy in Landau TheoryGibbs' free energy and Helmholtz free energyHow could chemical potential be interpreted as the molar Gibbs free energy?Gibbs Free Energy of Two concurring PhasesHelmholtz Free Energy at EquilibriumPhysical Significance of $U$ (Internal Energy ) , $H$ (Enthalpy) , $F$ (Free Energy) and $G$ (Gibbs Free Energy)?Gibbs free energy the 3 equation confusionIs Entropy a monotonically increasing function of Gibbs Free Energy/ Helmholtz free energy/ Enthalpy?













6












$begingroup$


The definition of enthalpy, $$H = U + PV,$$ assumes that the system is in a constant-pressure environment. Similarly, the definition of the Helmholtz free energy of the system, $$F = U - TS,$$ assumes a constant-temperature environment. The definition of the Gibbs free energy, $$G = U + PV - TS,$$ takes for granted both of the aformentioned assumptions. Does this mean, for example, that the enthalpy of a system is undefined for a system with a volume-dependent environmental pressure? I have similar questions about the Helmholtz free energy and the Gibbs free energy.










share|cite|improve this question











$endgroup$







  • 2




    $begingroup$
    I can understand where your puzzle comes from. Some textbook (such as Schroeder's book, section 5.1), for the convenience of presenting, uses phrases like constant pressure or constant temperature. But it doesn't exclude other conditions.
    $endgroup$
    – user115350
    2 days ago















6












$begingroup$


The definition of enthalpy, $$H = U + PV,$$ assumes that the system is in a constant-pressure environment. Similarly, the definition of the Helmholtz free energy of the system, $$F = U - TS,$$ assumes a constant-temperature environment. The definition of the Gibbs free energy, $$G = U + PV - TS,$$ takes for granted both of the aformentioned assumptions. Does this mean, for example, that the enthalpy of a system is undefined for a system with a volume-dependent environmental pressure? I have similar questions about the Helmholtz free energy and the Gibbs free energy.










share|cite|improve this question











$endgroup$







  • 2




    $begingroup$
    I can understand where your puzzle comes from. Some textbook (such as Schroeder's book, section 5.1), for the convenience of presenting, uses phrases like constant pressure or constant temperature. But it doesn't exclude other conditions.
    $endgroup$
    – user115350
    2 days ago













6












6








6


1



$begingroup$


The definition of enthalpy, $$H = U + PV,$$ assumes that the system is in a constant-pressure environment. Similarly, the definition of the Helmholtz free energy of the system, $$F = U - TS,$$ assumes a constant-temperature environment. The definition of the Gibbs free energy, $$G = U + PV - TS,$$ takes for granted both of the aformentioned assumptions. Does this mean, for example, that the enthalpy of a system is undefined for a system with a volume-dependent environmental pressure? I have similar questions about the Helmholtz free energy and the Gibbs free energy.










share|cite|improve this question











$endgroup$




The definition of enthalpy, $$H = U + PV,$$ assumes that the system is in a constant-pressure environment. Similarly, the definition of the Helmholtz free energy of the system, $$F = U - TS,$$ assumes a constant-temperature environment. The definition of the Gibbs free energy, $$G = U + PV - TS,$$ takes for granted both of the aformentioned assumptions. Does this mean, for example, that the enthalpy of a system is undefined for a system with a volume-dependent environmental pressure? I have similar questions about the Helmholtz free energy and the Gibbs free energy.







thermodynamics






share|cite|improve this question















share|cite|improve this question













share|cite|improve this question




share|cite|improve this question








edited 2 days ago







PiKindOfGuy

















asked 2 days ago









PiKindOfGuyPiKindOfGuy

701624




701624







  • 2




    $begingroup$
    I can understand where your puzzle comes from. Some textbook (such as Schroeder's book, section 5.1), for the convenience of presenting, uses phrases like constant pressure or constant temperature. But it doesn't exclude other conditions.
    $endgroup$
    – user115350
    2 days ago












  • 2




    $begingroup$
    I can understand where your puzzle comes from. Some textbook (such as Schroeder's book, section 5.1), for the convenience of presenting, uses phrases like constant pressure or constant temperature. But it doesn't exclude other conditions.
    $endgroup$
    – user115350
    2 days ago







2




2




$begingroup$
I can understand where your puzzle comes from. Some textbook (such as Schroeder's book, section 5.1), for the convenience of presenting, uses phrases like constant pressure or constant temperature. But it doesn't exclude other conditions.
$endgroup$
– user115350
2 days ago




$begingroup$
I can understand where your puzzle comes from. Some textbook (such as Schroeder's book, section 5.1), for the convenience of presenting, uses phrases like constant pressure or constant temperature. But it doesn't exclude other conditions.
$endgroup$
– user115350
2 days ago










3 Answers
3






active

oldest

votes


















7












$begingroup$

Those are the definitions of each. They don't assume anything about the system and can always be applied. You are getting mixed up with the scenarios in which they are usually applied since nice things happen. For example, for a system at constant pressure (and number of particles) $Delta H=Q$, where $Q$ is the heat that enters or leaves the system.



To add some more detail, this can be seen by substituting in the thermodynamic identity
$$text dU=Ttext dS-Ptext dV+mutext d N$$
into the differential of one of your thermodynamic potentials. For example, as mentioned above we have
$$text dH=text dU+Ptext dV+Vtext dP$$
so then
$$text dH=Ttext dS+Vtext dP+mutext dN$$
i.e. at constant pressure and number of particles $text dH=Ttext dS=text dQ$



You also say that the Gibbs free energy takes both mentioned assumptions "for granted", but see what happens if you do this process with the Gibbs free energy at constant temperature and pressure. It is a very important relation.



These processes are more generally called Legendre transformations






share|cite|improve this answer











$endgroup$












  • $begingroup$
    Sorry, I'm still confused. Are you claiming that if I don't assume anything about the environment those definitions still hold?
    $endgroup$
    – PiKindOfGuy
    2 days ago










  • $begingroup$
    @PiKindOfGuy Yes that is exactly right. As long as the system has well defined Pressure, Volume, Entropy, etc. then those definitions are fine. Why wouldn't they be? They are just definitions in terms of state variables. They don't refer to any processes. It is just how we define work to be $W=intmathbf Fcdottext dmathbf x$. As long as we have a force acting on an object over a distance the definition applies without any further assumptions of the system.
    $endgroup$
    – Aaron Stevens
    2 days ago










  • $begingroup$
    The pressure in those equations refers to the pressure of the environment, not that of the system, no? (See your comment.)
    $endgroup$
    – PiKindOfGuy
    2 days ago










  • $begingroup$
    @PiKindOfGuy We usually assume quasi-static processes where at any point in time the system is at equilibrium, so the pressure the system exerts on its boundary is the same as the pressure exerted on the system boundary by the environment
    $endgroup$
    – Aaron Stevens
    yesterday










  • $begingroup$
    @PiKindOfGuy Is there anything else I can do to make things more clear here?
    $endgroup$
    – Aaron Stevens
    10 hours ago



















0












$begingroup$

I agree with @Aaron Stevens. There are no built in assumptions of constant pressure or temperature in these definitions.



The Hemlholtz free energy, Gibbs free energy, Enthalpy and Internal Energy are sometimes referred to as thermodynamic potentials. For a discussion of these check out



http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/helmholtz.html



Hope this helps.






share|cite|improve this answer









$endgroup$




















    0












    $begingroup$

    It is important to keep separate definitions of thermodynamic potentials (TP) from the specific cases where one particular TP is more convenient than others.



    Let me use the Gibbs free energy $G$ as an example (the cases of Helmholtz free energy and enthalpy can be obtained by a parallel discussion).



    Let's start from the fact that the most convenient way of representing the internal energy $U$ of a fluid system as a function of the thermodynamic state is to use as independent variables the entropy $S$, the volume $V$ and the number of particles $N$. Such a choice does not imply any constraint on the system and in principle it is possible to use thermodynamic relations to express the same value of the internal energy as a function of different state variables (say $T$ and/or $P$). However, it turns out that only the description in terms of the set $S,V,T$ allows to encode the full thermodynamic behavior in one function of three variables. From this "privileged" choice of variables one can derive other descriptions using different state variables, but it is not possible to go the other way around. For instance, knowing $U(T,V,N)$ does not allow to reconstruct $U(S,V,N)$ (this is discussed in detail in Callen's textbook on Thermodynamics).



    The right way to change the independent variables while keeping the same information about the system as contained in $U(S,V,N)$ is to perform a Legendre transform (better a Legendre-Fenchel transform, due to the possibility of discontinuity of first derivatives).
    Legendre(-Fenchel) transforms of the internal energy are the so-called thermodynamic potentials.



    The Legendre transform to obtain the Gibbs free energy is briefly indicated as
    $$
    G = U -TS +PV
    $$

    Actually, the precise meaning of the above expression is that one starts with $U(S,V,N)$ and then $G$ is defined as
    $$
    G(T,P,N) = inf_S,V ( U(S,V,N) - TS + PV )
    $$

    Therefore, at level of definition, $T$ and $P$ are fixed just in the sense that one has to fix the values of the independent variables to identify the point where the function is evaluated. $T$ and $P$ can be changed at will and correspondingly one finds a value for $G$. Once one is using $T,P,N$ as independent variables, this does not imply that the conjugate variables $S,V,mu$ are not definite or do not have a precise value. Their values are fixed by the function $G$ and can be obtained by the relations
    $$S=-left.fracpartialGpartialTright|_P,N,~~~~
    V=left.fracpartialGpartialPright|_T,N, ~~~~
    mu=left.fracpartialGpartialNright|_T,P.$$



    After introducing thermodynamic potentials with their natural variables ($T,P,N$ for $G$), since the differential of each thermodynamic potentials is obviously a sum of therms multiplying the differential of the independent variables, in the case of $G$
    $$
    dG = -SdT + VdP + mu dN
    $$

    where $S=-left.fracpartialGpartialTright|_P,N$,
    $V=left.fracpartialGpartialPright|_T,N$ and
    $mu=left.fracpartialGpartialNright|_T,P$.



    Therefore, in the case of a transformation keeping constant some of the variables $T,P,N$ one gets a simplified formula with respect to the full differential.






    share|cite|improve this answer









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      3 Answers
      3






      active

      oldest

      votes








      3 Answers
      3






      active

      oldest

      votes









      active

      oldest

      votes






      active

      oldest

      votes









      7












      $begingroup$

      Those are the definitions of each. They don't assume anything about the system and can always be applied. You are getting mixed up with the scenarios in which they are usually applied since nice things happen. For example, for a system at constant pressure (and number of particles) $Delta H=Q$, where $Q$ is the heat that enters or leaves the system.



      To add some more detail, this can be seen by substituting in the thermodynamic identity
      $$text dU=Ttext dS-Ptext dV+mutext d N$$
      into the differential of one of your thermodynamic potentials. For example, as mentioned above we have
      $$text dH=text dU+Ptext dV+Vtext dP$$
      so then
      $$text dH=Ttext dS+Vtext dP+mutext dN$$
      i.e. at constant pressure and number of particles $text dH=Ttext dS=text dQ$



      You also say that the Gibbs free energy takes both mentioned assumptions "for granted", but see what happens if you do this process with the Gibbs free energy at constant temperature and pressure. It is a very important relation.



      These processes are more generally called Legendre transformations






      share|cite|improve this answer











      $endgroup$












      • $begingroup$
        Sorry, I'm still confused. Are you claiming that if I don't assume anything about the environment those definitions still hold?
        $endgroup$
        – PiKindOfGuy
        2 days ago










      • $begingroup$
        @PiKindOfGuy Yes that is exactly right. As long as the system has well defined Pressure, Volume, Entropy, etc. then those definitions are fine. Why wouldn't they be? They are just definitions in terms of state variables. They don't refer to any processes. It is just how we define work to be $W=intmathbf Fcdottext dmathbf x$. As long as we have a force acting on an object over a distance the definition applies without any further assumptions of the system.
        $endgroup$
        – Aaron Stevens
        2 days ago










      • $begingroup$
        The pressure in those equations refers to the pressure of the environment, not that of the system, no? (See your comment.)
        $endgroup$
        – PiKindOfGuy
        2 days ago










      • $begingroup$
        @PiKindOfGuy We usually assume quasi-static processes where at any point in time the system is at equilibrium, so the pressure the system exerts on its boundary is the same as the pressure exerted on the system boundary by the environment
        $endgroup$
        – Aaron Stevens
        yesterday










      • $begingroup$
        @PiKindOfGuy Is there anything else I can do to make things more clear here?
        $endgroup$
        – Aaron Stevens
        10 hours ago
















      7












      $begingroup$

      Those are the definitions of each. They don't assume anything about the system and can always be applied. You are getting mixed up with the scenarios in which they are usually applied since nice things happen. For example, for a system at constant pressure (and number of particles) $Delta H=Q$, where $Q$ is the heat that enters or leaves the system.



      To add some more detail, this can be seen by substituting in the thermodynamic identity
      $$text dU=Ttext dS-Ptext dV+mutext d N$$
      into the differential of one of your thermodynamic potentials. For example, as mentioned above we have
      $$text dH=text dU+Ptext dV+Vtext dP$$
      so then
      $$text dH=Ttext dS+Vtext dP+mutext dN$$
      i.e. at constant pressure and number of particles $text dH=Ttext dS=text dQ$



      You also say that the Gibbs free energy takes both mentioned assumptions "for granted", but see what happens if you do this process with the Gibbs free energy at constant temperature and pressure. It is a very important relation.



      These processes are more generally called Legendre transformations






      share|cite|improve this answer











      $endgroup$












      • $begingroup$
        Sorry, I'm still confused. Are you claiming that if I don't assume anything about the environment those definitions still hold?
        $endgroup$
        – PiKindOfGuy
        2 days ago










      • $begingroup$
        @PiKindOfGuy Yes that is exactly right. As long as the system has well defined Pressure, Volume, Entropy, etc. then those definitions are fine. Why wouldn't they be? They are just definitions in terms of state variables. They don't refer to any processes. It is just how we define work to be $W=intmathbf Fcdottext dmathbf x$. As long as we have a force acting on an object over a distance the definition applies without any further assumptions of the system.
        $endgroup$
        – Aaron Stevens
        2 days ago










      • $begingroup$
        The pressure in those equations refers to the pressure of the environment, not that of the system, no? (See your comment.)
        $endgroup$
        – PiKindOfGuy
        2 days ago










      • $begingroup$
        @PiKindOfGuy We usually assume quasi-static processes where at any point in time the system is at equilibrium, so the pressure the system exerts on its boundary is the same as the pressure exerted on the system boundary by the environment
        $endgroup$
        – Aaron Stevens
        yesterday










      • $begingroup$
        @PiKindOfGuy Is there anything else I can do to make things more clear here?
        $endgroup$
        – Aaron Stevens
        10 hours ago














      7












      7








      7





      $begingroup$

      Those are the definitions of each. They don't assume anything about the system and can always be applied. You are getting mixed up with the scenarios in which they are usually applied since nice things happen. For example, for a system at constant pressure (and number of particles) $Delta H=Q$, where $Q$ is the heat that enters or leaves the system.



      To add some more detail, this can be seen by substituting in the thermodynamic identity
      $$text dU=Ttext dS-Ptext dV+mutext d N$$
      into the differential of one of your thermodynamic potentials. For example, as mentioned above we have
      $$text dH=text dU+Ptext dV+Vtext dP$$
      so then
      $$text dH=Ttext dS+Vtext dP+mutext dN$$
      i.e. at constant pressure and number of particles $text dH=Ttext dS=text dQ$



      You also say that the Gibbs free energy takes both mentioned assumptions "for granted", but see what happens if you do this process with the Gibbs free energy at constant temperature and pressure. It is a very important relation.



      These processes are more generally called Legendre transformations






      share|cite|improve this answer











      $endgroup$



      Those are the definitions of each. They don't assume anything about the system and can always be applied. You are getting mixed up with the scenarios in which they are usually applied since nice things happen. For example, for a system at constant pressure (and number of particles) $Delta H=Q$, where $Q$ is the heat that enters or leaves the system.



      To add some more detail, this can be seen by substituting in the thermodynamic identity
      $$text dU=Ttext dS-Ptext dV+mutext d N$$
      into the differential of one of your thermodynamic potentials. For example, as mentioned above we have
      $$text dH=text dU+Ptext dV+Vtext dP$$
      so then
      $$text dH=Ttext dS+Vtext dP+mutext dN$$
      i.e. at constant pressure and number of particles $text dH=Ttext dS=text dQ$



      You also say that the Gibbs free energy takes both mentioned assumptions "for granted", but see what happens if you do this process with the Gibbs free energy at constant temperature and pressure. It is a very important relation.



      These processes are more generally called Legendre transformations







      share|cite|improve this answer














      share|cite|improve this answer



      share|cite|improve this answer








      edited 2 days ago

























      answered 2 days ago









      Aaron StevensAaron Stevens

      14.2k42252




      14.2k42252











      • $begingroup$
        Sorry, I'm still confused. Are you claiming that if I don't assume anything about the environment those definitions still hold?
        $endgroup$
        – PiKindOfGuy
        2 days ago










      • $begingroup$
        @PiKindOfGuy Yes that is exactly right. As long as the system has well defined Pressure, Volume, Entropy, etc. then those definitions are fine. Why wouldn't they be? They are just definitions in terms of state variables. They don't refer to any processes. It is just how we define work to be $W=intmathbf Fcdottext dmathbf x$. As long as we have a force acting on an object over a distance the definition applies without any further assumptions of the system.
        $endgroup$
        – Aaron Stevens
        2 days ago










      • $begingroup$
        The pressure in those equations refers to the pressure of the environment, not that of the system, no? (See your comment.)
        $endgroup$
        – PiKindOfGuy
        2 days ago










      • $begingroup$
        @PiKindOfGuy We usually assume quasi-static processes where at any point in time the system is at equilibrium, so the pressure the system exerts on its boundary is the same as the pressure exerted on the system boundary by the environment
        $endgroup$
        – Aaron Stevens
        yesterday










      • $begingroup$
        @PiKindOfGuy Is there anything else I can do to make things more clear here?
        $endgroup$
        – Aaron Stevens
        10 hours ago

















      • $begingroup$
        Sorry, I'm still confused. Are you claiming that if I don't assume anything about the environment those definitions still hold?
        $endgroup$
        – PiKindOfGuy
        2 days ago










      • $begingroup$
        @PiKindOfGuy Yes that is exactly right. As long as the system has well defined Pressure, Volume, Entropy, etc. then those definitions are fine. Why wouldn't they be? They are just definitions in terms of state variables. They don't refer to any processes. It is just how we define work to be $W=intmathbf Fcdottext dmathbf x$. As long as we have a force acting on an object over a distance the definition applies without any further assumptions of the system.
        $endgroup$
        – Aaron Stevens
        2 days ago










      • $begingroup$
        The pressure in those equations refers to the pressure of the environment, not that of the system, no? (See your comment.)
        $endgroup$
        – PiKindOfGuy
        2 days ago










      • $begingroup$
        @PiKindOfGuy We usually assume quasi-static processes where at any point in time the system is at equilibrium, so the pressure the system exerts on its boundary is the same as the pressure exerted on the system boundary by the environment
        $endgroup$
        – Aaron Stevens
        yesterday










      • $begingroup$
        @PiKindOfGuy Is there anything else I can do to make things more clear here?
        $endgroup$
        – Aaron Stevens
        10 hours ago
















      $begingroup$
      Sorry, I'm still confused. Are you claiming that if I don't assume anything about the environment those definitions still hold?
      $endgroup$
      – PiKindOfGuy
      2 days ago




      $begingroup$
      Sorry, I'm still confused. Are you claiming that if I don't assume anything about the environment those definitions still hold?
      $endgroup$
      – PiKindOfGuy
      2 days ago












      $begingroup$
      @PiKindOfGuy Yes that is exactly right. As long as the system has well defined Pressure, Volume, Entropy, etc. then those definitions are fine. Why wouldn't they be? They are just definitions in terms of state variables. They don't refer to any processes. It is just how we define work to be $W=intmathbf Fcdottext dmathbf x$. As long as we have a force acting on an object over a distance the definition applies without any further assumptions of the system.
      $endgroup$
      – Aaron Stevens
      2 days ago




      $begingroup$
      @PiKindOfGuy Yes that is exactly right. As long as the system has well defined Pressure, Volume, Entropy, etc. then those definitions are fine. Why wouldn't they be? They are just definitions in terms of state variables. They don't refer to any processes. It is just how we define work to be $W=intmathbf Fcdottext dmathbf x$. As long as we have a force acting on an object over a distance the definition applies without any further assumptions of the system.
      $endgroup$
      – Aaron Stevens
      2 days ago












      $begingroup$
      The pressure in those equations refers to the pressure of the environment, not that of the system, no? (See your comment.)
      $endgroup$
      – PiKindOfGuy
      2 days ago




      $begingroup$
      The pressure in those equations refers to the pressure of the environment, not that of the system, no? (See your comment.)
      $endgroup$
      – PiKindOfGuy
      2 days ago












      $begingroup$
      @PiKindOfGuy We usually assume quasi-static processes where at any point in time the system is at equilibrium, so the pressure the system exerts on its boundary is the same as the pressure exerted on the system boundary by the environment
      $endgroup$
      – Aaron Stevens
      yesterday




      $begingroup$
      @PiKindOfGuy We usually assume quasi-static processes where at any point in time the system is at equilibrium, so the pressure the system exerts on its boundary is the same as the pressure exerted on the system boundary by the environment
      $endgroup$
      – Aaron Stevens
      yesterday












      $begingroup$
      @PiKindOfGuy Is there anything else I can do to make things more clear here?
      $endgroup$
      – Aaron Stevens
      10 hours ago





      $begingroup$
      @PiKindOfGuy Is there anything else I can do to make things more clear here?
      $endgroup$
      – Aaron Stevens
      10 hours ago












      0












      $begingroup$

      I agree with @Aaron Stevens. There are no built in assumptions of constant pressure or temperature in these definitions.



      The Hemlholtz free energy, Gibbs free energy, Enthalpy and Internal Energy are sometimes referred to as thermodynamic potentials. For a discussion of these check out



      http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/helmholtz.html



      Hope this helps.






      share|cite|improve this answer









      $endgroup$

















        0












        $begingroup$

        I agree with @Aaron Stevens. There are no built in assumptions of constant pressure or temperature in these definitions.



        The Hemlholtz free energy, Gibbs free energy, Enthalpy and Internal Energy are sometimes referred to as thermodynamic potentials. For a discussion of these check out



        http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/helmholtz.html



        Hope this helps.






        share|cite|improve this answer









        $endgroup$















          0












          0








          0





          $begingroup$

          I agree with @Aaron Stevens. There are no built in assumptions of constant pressure or temperature in these definitions.



          The Hemlholtz free energy, Gibbs free energy, Enthalpy and Internal Energy are sometimes referred to as thermodynamic potentials. For a discussion of these check out



          http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/helmholtz.html



          Hope this helps.






          share|cite|improve this answer









          $endgroup$



          I agree with @Aaron Stevens. There are no built in assumptions of constant pressure or temperature in these definitions.



          The Hemlholtz free energy, Gibbs free energy, Enthalpy and Internal Energy are sometimes referred to as thermodynamic potentials. For a discussion of these check out



          http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/helmholtz.html



          Hope this helps.







          share|cite|improve this answer












          share|cite|improve this answer



          share|cite|improve this answer










          answered 2 days ago









          Bob DBob D

          4,4052318




          4,4052318





















              0












              $begingroup$

              It is important to keep separate definitions of thermodynamic potentials (TP) from the specific cases where one particular TP is more convenient than others.



              Let me use the Gibbs free energy $G$ as an example (the cases of Helmholtz free energy and enthalpy can be obtained by a parallel discussion).



              Let's start from the fact that the most convenient way of representing the internal energy $U$ of a fluid system as a function of the thermodynamic state is to use as independent variables the entropy $S$, the volume $V$ and the number of particles $N$. Such a choice does not imply any constraint on the system and in principle it is possible to use thermodynamic relations to express the same value of the internal energy as a function of different state variables (say $T$ and/or $P$). However, it turns out that only the description in terms of the set $S,V,T$ allows to encode the full thermodynamic behavior in one function of three variables. From this "privileged" choice of variables one can derive other descriptions using different state variables, but it is not possible to go the other way around. For instance, knowing $U(T,V,N)$ does not allow to reconstruct $U(S,V,N)$ (this is discussed in detail in Callen's textbook on Thermodynamics).



              The right way to change the independent variables while keeping the same information about the system as contained in $U(S,V,N)$ is to perform a Legendre transform (better a Legendre-Fenchel transform, due to the possibility of discontinuity of first derivatives).
              Legendre(-Fenchel) transforms of the internal energy are the so-called thermodynamic potentials.



              The Legendre transform to obtain the Gibbs free energy is briefly indicated as
              $$
              G = U -TS +PV
              $$

              Actually, the precise meaning of the above expression is that one starts with $U(S,V,N)$ and then $G$ is defined as
              $$
              G(T,P,N) = inf_S,V ( U(S,V,N) - TS + PV )
              $$

              Therefore, at level of definition, $T$ and $P$ are fixed just in the sense that one has to fix the values of the independent variables to identify the point where the function is evaluated. $T$ and $P$ can be changed at will and correspondingly one finds a value for $G$. Once one is using $T,P,N$ as independent variables, this does not imply that the conjugate variables $S,V,mu$ are not definite or do not have a precise value. Their values are fixed by the function $G$ and can be obtained by the relations
              $$S=-left.fracpartialGpartialTright|_P,N,~~~~
              V=left.fracpartialGpartialPright|_T,N, ~~~~
              mu=left.fracpartialGpartialNright|_T,P.$$



              After introducing thermodynamic potentials with their natural variables ($T,P,N$ for $G$), since the differential of each thermodynamic potentials is obviously a sum of therms multiplying the differential of the independent variables, in the case of $G$
              $$
              dG = -SdT + VdP + mu dN
              $$

              where $S=-left.fracpartialGpartialTright|_P,N$,
              $V=left.fracpartialGpartialPright|_T,N$ and
              $mu=left.fracpartialGpartialNright|_T,P$.



              Therefore, in the case of a transformation keeping constant some of the variables $T,P,N$ one gets a simplified formula with respect to the full differential.






              share|cite|improve this answer









              $endgroup$

















                0












                $begingroup$

                It is important to keep separate definitions of thermodynamic potentials (TP) from the specific cases where one particular TP is more convenient than others.



                Let me use the Gibbs free energy $G$ as an example (the cases of Helmholtz free energy and enthalpy can be obtained by a parallel discussion).



                Let's start from the fact that the most convenient way of representing the internal energy $U$ of a fluid system as a function of the thermodynamic state is to use as independent variables the entropy $S$, the volume $V$ and the number of particles $N$. Such a choice does not imply any constraint on the system and in principle it is possible to use thermodynamic relations to express the same value of the internal energy as a function of different state variables (say $T$ and/or $P$). However, it turns out that only the description in terms of the set $S,V,T$ allows to encode the full thermodynamic behavior in one function of three variables. From this "privileged" choice of variables one can derive other descriptions using different state variables, but it is not possible to go the other way around. For instance, knowing $U(T,V,N)$ does not allow to reconstruct $U(S,V,N)$ (this is discussed in detail in Callen's textbook on Thermodynamics).



                The right way to change the independent variables while keeping the same information about the system as contained in $U(S,V,N)$ is to perform a Legendre transform (better a Legendre-Fenchel transform, due to the possibility of discontinuity of first derivatives).
                Legendre(-Fenchel) transforms of the internal energy are the so-called thermodynamic potentials.



                The Legendre transform to obtain the Gibbs free energy is briefly indicated as
                $$
                G = U -TS +PV
                $$

                Actually, the precise meaning of the above expression is that one starts with $U(S,V,N)$ and then $G$ is defined as
                $$
                G(T,P,N) = inf_S,V ( U(S,V,N) - TS + PV )
                $$

                Therefore, at level of definition, $T$ and $P$ are fixed just in the sense that one has to fix the values of the independent variables to identify the point where the function is evaluated. $T$ and $P$ can be changed at will and correspondingly one finds a value for $G$. Once one is using $T,P,N$ as independent variables, this does not imply that the conjugate variables $S,V,mu$ are not definite or do not have a precise value. Their values are fixed by the function $G$ and can be obtained by the relations
                $$S=-left.fracpartialGpartialTright|_P,N,~~~~
                V=left.fracpartialGpartialPright|_T,N, ~~~~
                mu=left.fracpartialGpartialNright|_T,P.$$



                After introducing thermodynamic potentials with their natural variables ($T,P,N$ for $G$), since the differential of each thermodynamic potentials is obviously a sum of therms multiplying the differential of the independent variables, in the case of $G$
                $$
                dG = -SdT + VdP + mu dN
                $$

                where $S=-left.fracpartialGpartialTright|_P,N$,
                $V=left.fracpartialGpartialPright|_T,N$ and
                $mu=left.fracpartialGpartialNright|_T,P$.



                Therefore, in the case of a transformation keeping constant some of the variables $T,P,N$ one gets a simplified formula with respect to the full differential.






                share|cite|improve this answer









                $endgroup$















                  0












                  0








                  0





                  $begingroup$

                  It is important to keep separate definitions of thermodynamic potentials (TP) from the specific cases where one particular TP is more convenient than others.



                  Let me use the Gibbs free energy $G$ as an example (the cases of Helmholtz free energy and enthalpy can be obtained by a parallel discussion).



                  Let's start from the fact that the most convenient way of representing the internal energy $U$ of a fluid system as a function of the thermodynamic state is to use as independent variables the entropy $S$, the volume $V$ and the number of particles $N$. Such a choice does not imply any constraint on the system and in principle it is possible to use thermodynamic relations to express the same value of the internal energy as a function of different state variables (say $T$ and/or $P$). However, it turns out that only the description in terms of the set $S,V,T$ allows to encode the full thermodynamic behavior in one function of three variables. From this "privileged" choice of variables one can derive other descriptions using different state variables, but it is not possible to go the other way around. For instance, knowing $U(T,V,N)$ does not allow to reconstruct $U(S,V,N)$ (this is discussed in detail in Callen's textbook on Thermodynamics).



                  The right way to change the independent variables while keeping the same information about the system as contained in $U(S,V,N)$ is to perform a Legendre transform (better a Legendre-Fenchel transform, due to the possibility of discontinuity of first derivatives).
                  Legendre(-Fenchel) transforms of the internal energy are the so-called thermodynamic potentials.



                  The Legendre transform to obtain the Gibbs free energy is briefly indicated as
                  $$
                  G = U -TS +PV
                  $$

                  Actually, the precise meaning of the above expression is that one starts with $U(S,V,N)$ and then $G$ is defined as
                  $$
                  G(T,P,N) = inf_S,V ( U(S,V,N) - TS + PV )
                  $$

                  Therefore, at level of definition, $T$ and $P$ are fixed just in the sense that one has to fix the values of the independent variables to identify the point where the function is evaluated. $T$ and $P$ can be changed at will and correspondingly one finds a value for $G$. Once one is using $T,P,N$ as independent variables, this does not imply that the conjugate variables $S,V,mu$ are not definite or do not have a precise value. Their values are fixed by the function $G$ and can be obtained by the relations
                  $$S=-left.fracpartialGpartialTright|_P,N,~~~~
                  V=left.fracpartialGpartialPright|_T,N, ~~~~
                  mu=left.fracpartialGpartialNright|_T,P.$$



                  After introducing thermodynamic potentials with their natural variables ($T,P,N$ for $G$), since the differential of each thermodynamic potentials is obviously a sum of therms multiplying the differential of the independent variables, in the case of $G$
                  $$
                  dG = -SdT + VdP + mu dN
                  $$

                  where $S=-left.fracpartialGpartialTright|_P,N$,
                  $V=left.fracpartialGpartialPright|_T,N$ and
                  $mu=left.fracpartialGpartialNright|_T,P$.



                  Therefore, in the case of a transformation keeping constant some of the variables $T,P,N$ one gets a simplified formula with respect to the full differential.






                  share|cite|improve this answer









                  $endgroup$



                  It is important to keep separate definitions of thermodynamic potentials (TP) from the specific cases where one particular TP is more convenient than others.



                  Let me use the Gibbs free energy $G$ as an example (the cases of Helmholtz free energy and enthalpy can be obtained by a parallel discussion).



                  Let's start from the fact that the most convenient way of representing the internal energy $U$ of a fluid system as a function of the thermodynamic state is to use as independent variables the entropy $S$, the volume $V$ and the number of particles $N$. Such a choice does not imply any constraint on the system and in principle it is possible to use thermodynamic relations to express the same value of the internal energy as a function of different state variables (say $T$ and/or $P$). However, it turns out that only the description in terms of the set $S,V,T$ allows to encode the full thermodynamic behavior in one function of three variables. From this "privileged" choice of variables one can derive other descriptions using different state variables, but it is not possible to go the other way around. For instance, knowing $U(T,V,N)$ does not allow to reconstruct $U(S,V,N)$ (this is discussed in detail in Callen's textbook on Thermodynamics).



                  The right way to change the independent variables while keeping the same information about the system as contained in $U(S,V,N)$ is to perform a Legendre transform (better a Legendre-Fenchel transform, due to the possibility of discontinuity of first derivatives).
                  Legendre(-Fenchel) transforms of the internal energy are the so-called thermodynamic potentials.



                  The Legendre transform to obtain the Gibbs free energy is briefly indicated as
                  $$
                  G = U -TS +PV
                  $$

                  Actually, the precise meaning of the above expression is that one starts with $U(S,V,N)$ and then $G$ is defined as
                  $$
                  G(T,P,N) = inf_S,V ( U(S,V,N) - TS + PV )
                  $$

                  Therefore, at level of definition, $T$ and $P$ are fixed just in the sense that one has to fix the values of the independent variables to identify the point where the function is evaluated. $T$ and $P$ can be changed at will and correspondingly one finds a value for $G$. Once one is using $T,P,N$ as independent variables, this does not imply that the conjugate variables $S,V,mu$ are not definite or do not have a precise value. Their values are fixed by the function $G$ and can be obtained by the relations
                  $$S=-left.fracpartialGpartialTright|_P,N,~~~~
                  V=left.fracpartialGpartialPright|_T,N, ~~~~
                  mu=left.fracpartialGpartialNright|_T,P.$$



                  After introducing thermodynamic potentials with their natural variables ($T,P,N$ for $G$), since the differential of each thermodynamic potentials is obviously a sum of therms multiplying the differential of the independent variables, in the case of $G$
                  $$
                  dG = -SdT + VdP + mu dN
                  $$

                  where $S=-left.fracpartialGpartialTright|_P,N$,
                  $V=left.fracpartialGpartialPright|_T,N$ and
                  $mu=left.fracpartialGpartialNright|_T,P$.



                  Therefore, in the case of a transformation keeping constant some of the variables $T,P,N$ one gets a simplified formula with respect to the full differential.







                  share|cite|improve this answer












                  share|cite|improve this answer



                  share|cite|improve this answer










                  answered yesterday









                  GiorgioPGiorgioP

                  4,2501628




                  4,2501628



























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                      대한민국 목차 국명 지리 역사 정치 국방 경제 사회 문화 국제 순위 관련 항목 각주 외부 링크 둘러보기 메뉴북위 37° 34′ 08″ 동경 126° 58′ 36″ / 북위 37.568889° 동경 126.976667°  / 37.568889; 126.976667ehThe Korean Repository문단을 편집문단을 편집추가해Clarkson PLC 사Report for Selected Countries and Subjects-Korea“Human Development Index and its components: P.198”“http://www.law.go.kr/%EB%B2%95%EB%A0%B9/%EB%8C%80%ED%95%9C%EB%AF%BC%EA%B5%AD%EA%B5%AD%EA%B8%B0%EB%B2%95”"한국은 국제법상 한반도 유일 합법정부 아니다" - 오마이뉴스 모바일Report for Selected Countries and Subjects: South Korea격동의 역사와 함께한 조선일보 90년 : 조선일보 인수해 혁신시킨 신석우, 임시정부 때는 '대한민국' 국호(國號) 정해《우리가 몰랐던 우리 역사: 나라 이름의 비밀을 찾아가는 역사 여행》“남북 공식호칭 ‘남한’‘북한’으로 쓴다”“Corea 대 Korea, 누가 이긴 거야?”국내기후자료 - 한국[김대중 前 대통령 서거] 과감한 구조개혁 'DJ노믹스'로 최단기간 환란극복 :: 네이버 뉴스“이라크 "韓-쿠르드 유전개발 MOU 승인 안해"(종합)”“해외 우리국민 추방사례 43%가 일본”차기전차 K2'흑표'의 세계 최고 전력 분석, 쿠키뉴스 엄기영, 2007-03-02두산인프라, 헬기잡는 장갑차 'K21'...내년부터 공급, 고뉴스 이대준, 2008-10-30과거 내용 찾기mk 뉴스 - 구매력 기준으로 보면 한국 1인당 소득 3만弗과거 내용 찾기"The N-11: More Than an Acronym"Archived조선일보 최우석, 2008-11-01Global 500 2008: Countries - South Korea“몇년째 '시한폭탄'... 가계부채, 올해는 터질까”가구당 부채 5000만원 처음 넘어서“‘빚’으로 내몰리는 사회.. 위기의 가계대출”“[경제365] 공공부문 부채 급증…800조 육박”“"소득 양극화 다소 완화...불평등은 여전"”“공정사회·공생발전 한참 멀었네”iSuppli,08年2QのDRAMシェア・ランキングを発表(08/8/11)South Korea dominates shipbuilding industry | Stock Market News & Stocks to Watch from StraightStocks한국 자동차 생산, 3년 연속 세계 5위자동차수출 '현대-삼성 웃고 기아-대우-쌍용은 울고' 과거 내용 찾기동반성장위 창립 1주년 맞아Archived"중기적합 3개업종 합의 무시한 채 선정"李대통령, 사업 무분별 확장 소상공인 생계 위협 질타삼성-LG, 서민업종인 빵·분식사업 잇따라 철수상생은 뒷전…SSM ‘몸집 불리기’ 혈안Archived“경부고속도에 '아시안하이웨이' 표지판”'철의 실크로드' 앞서 '말(言)의 실크로드'부터, 프레시안 정창현, 2008-10-01“'서울 지하철은 안전한가?'”“서울시 “올해 안에 모든 지하철역 스크린도어 설치””“부산지하철 1,2호선 승강장 안전펜스 설치 완료”“전교조, 정부 노조 통계서 처음 빠져”“[Weekly BIZ] 도요타 '제로 이사회'가 리콜 사태 불러들였다”“S Korea slams high tuition costs”““정치가 여론 양극화 부채질… 합리주의 절실””“〈"`촛불집회'는 민주주의의 질적 변화 상징"〉”““촛불집회가 민주주의 왜곡 초래””“국민 65%, "한국 노사관계 대립적"”“한국 국가경쟁력 27위‥노사관계 '꼴찌'”“제대로 형성되지 않은 대한민국 이념지형”“[신년기획-갈등의 시대] 갈등지수 OECD 4위…사회적 손실 GDP 27% 무려 300조”“2012 총선-대선의 키워드는 '국민과 소통'”“한국 삶의 질 27위, 2000년과 2008년 연속 하위권 머물러”“[해피 코리아] 행복점수 68점…해외 평가선 '낙제점'”“한국 어린이·청소년 행복지수 3년 연속 OECD ‘꼴찌’”“한국 이혼율 OECD중 8위”“[통계청] 한국 이혼율 OECD 4위”“오피니언 [이렇게 생각한다] `부부의 날` 에 돌아본 이혼율 1위 한국”“Suicide Rates by Country, Global Health Observatory Data Repository.”“1. 또 다른 차별”“오피니언 [편집자에게] '왕따'와 '패거리 정치' 심리는 닮은꼴”“[미래한국리포트] 무한경쟁에 빠진 대한민국”“대학생 98% "외모가 경쟁력이라는 말 동의"”“특급호텔 웨딩·200만원대 유모차… "남보다 더…" 호화病, 고질병 됐다”“[스트레스 공화국] ① 경쟁사회, 스트레스 쌓인다”““매일 30여명 자살 한국, 의사보다 무속인에…””“"자살 부르는 '우울증', 환자 중 85% 치료 안 받아"”“정신병원을 가다”“대한민국도 ‘묻지마 범죄’,안전지대 아니다”“유엔 "학생 '성적 지향'에 따른 차별 금지하라"”“유엔아동권리위원회 보고서 및 번역본 원문”“고졸 성공스토리 담은 '제빵왕 김탁구' 드라마 나온다”“‘빛 좋은 개살구’ 고졸 취업…실습 대신 착취”원본 문서“정신건강, 사회적 편견부터 고쳐드립니다”‘소통’과 ‘행복’에 목 마른 사회가 잠들어 있던 ‘심리학’ 깨웠다“[포토] 사유리-곽금주 교수의 유쾌한 심리상담”“"올해 한국인 평균 영화관람횟수 세계 1위"(종합)”“[게임연중기획] 게임은 문화다-여가활동 1순위 게임”“영화속 ‘영어 지상주의’ …“왠지 씁쓸한데””“2월 `신문 부수 인증기관` 지정..방송법 후속작업”“무료신문 성장동력 ‘차별성’과 ‘갈등해소’”대한민국 국회 법률지식정보시스템"Pew Research Center's Religion & Public Life Project: South Korea"“amp;vwcd=MT_ZTITLE&path=인구·가구%20>%20인구총조사%20>%20인구부문%20>%20 총조사인구(2005)%20>%20전수부문&oper_YN=Y&item=&keyword=종교별%20인구& amp;lang_mode=kor&list_id= 2005년 통계청 인구 총조사”원본 문서“한국인이 좋아하는 취미와 운동 (2004-2009)”“한국인이 좋아하는 취미와 운동 (2004-2014)”Archived“한국, `부분적 언론자유국' 강등〈프리덤하우스〉”“국경없는기자회 "한국, 인터넷감시 대상국"”“한국, 조선산업 1위 유지(S. Korea Stays Top Shipbuilding Nation) RZD-Partner Portal”원본 문서“한국, 4년 만에 ‘선박건조 1위’”“옛 마산시,인터넷속도 세계 1위”“"한국 초고속 인터넷망 세계1위"”“인터넷·휴대폰 요금, 외국보다 훨씬 비싸”“한국 관세행정 6년 연속 세계 '1위'”“한국 교통사고 사망자 수 OECD 회원국 중 2위”“결핵 후진국' 한국, 환자가 급증한 이유는”“수술은 신중해야… 자칫하면 생명 위협”대한민국분류대한민국의 지도대한민국 정부대표 다국어포털대한민국 전자정부대한민국 국회한국방송공사about korea and information korea브리태니커 백과사전(한국편)론리플래닛의 정보(한국편)CIA의 세계 정보(한국편)마리암 부디아 (Mariam Budia),『한국: 하늘이 내린 한 폭의 그림』, 서울: 트랜스라틴 19호 (2012년 3월)대한민국ehehehehehehehehehehehehehehWorldCat132441370n791268020000 0001 2308 81034078029-6026373548cb11863345f(데이터)00573706ge128495