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Thermodynamic potential
A thermodynamic potential (or more accurately, a thermodynamic potential energy) is a scalar quantity used to represent the thermodynamic state of a system. Just as in mechanics, where potential energy is defined as capacity to do work, similarly different potentials have different meanings. The concept of thermodynamic potentials was introduced by Pierre Duhem in 1886. Josiah Willard Gibbs in his papers used the term fundamental functions. Effects of changes in thermodynamic potentials can sometimes be measured directly, while their absolute magnitudes can only be assessed using computational chemistry or similar methods.
One main thermodynamic potential that has a physical interpretation is the internal energy U. It is the energy of configuration of a given system of conservative forces (that is why it is called potential) and only has meaning with respect to a defined set of references (or data). Expressions for all other thermodynamic energy potentials are derivable via Legendre transforms from an expression for U. In other words, each thermodynamic potential is equivalent to other thermodynamic potentials; each potential is a different expression of the others.
In thermodynamics, external forces, such as gravity, are counted as contributing to total energy rather than to thermodynamic potentials. For example, the working fluid in a steam engine sitting on top of Mount Everest has higher total energy due to gravity than it has at the bottom of the Mariana Trench, but the same thermodynamic potentials. This is because the gravitational potential energy belongs to the total energy rather than to thermodynamic potentials such as internal energy.
Five common thermodynamic potentials are:
where T = temperature, S = entropy, p = pressure, V = volume. Ni is the number of particles of type i in the system and μi is the chemical potential for an i-type particle. The set of all Ni are also included as natural variables but may be ignored when no chemical reactions are occurring which cause them to change. The Helmholtz free energy is in ISO/IEC standard called Helmholtz energy or Helmholtz function. It is often denoted by the symbol F, but the use of A is preferred by IUPAC, ISO and IEC.
These five common potentials are all potential energies, but there are also entropy potentials. The thermodynamic square can be used as a tool to recall and derive some of the potentials.
Just as in mechanics, where potential energy is defined as capacity to do work, similarly different potentials have different meanings like the below:
From these meanings (which actually apply in specific conditions, e.g. constant pressure, temperature, etc.), for positive changes (e.g., ΔU > 0), we can say that ΔU is the energy added to the system, ΔF is the total work done on it, ΔG is the non-mechanical work done on it, and ΔH is the sum of non-mechanical work done on the system and the heat given to it.
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Thermodynamic potential
A thermodynamic potential (or more accurately, a thermodynamic potential energy) is a scalar quantity used to represent the thermodynamic state of a system. Just as in mechanics, where potential energy is defined as capacity to do work, similarly different potentials have different meanings. The concept of thermodynamic potentials was introduced by Pierre Duhem in 1886. Josiah Willard Gibbs in his papers used the term fundamental functions. Effects of changes in thermodynamic potentials can sometimes be measured directly, while their absolute magnitudes can only be assessed using computational chemistry or similar methods.
One main thermodynamic potential that has a physical interpretation is the internal energy U. It is the energy of configuration of a given system of conservative forces (that is why it is called potential) and only has meaning with respect to a defined set of references (or data). Expressions for all other thermodynamic energy potentials are derivable via Legendre transforms from an expression for U. In other words, each thermodynamic potential is equivalent to other thermodynamic potentials; each potential is a different expression of the others.
In thermodynamics, external forces, such as gravity, are counted as contributing to total energy rather than to thermodynamic potentials. For example, the working fluid in a steam engine sitting on top of Mount Everest has higher total energy due to gravity than it has at the bottom of the Mariana Trench, but the same thermodynamic potentials. This is because the gravitational potential energy belongs to the total energy rather than to thermodynamic potentials such as internal energy.
Five common thermodynamic potentials are:
where T = temperature, S = entropy, p = pressure, V = volume. Ni is the number of particles of type i in the system and μi is the chemical potential for an i-type particle. The set of all Ni are also included as natural variables but may be ignored when no chemical reactions are occurring which cause them to change. The Helmholtz free energy is in ISO/IEC standard called Helmholtz energy or Helmholtz function. It is often denoted by the symbol F, but the use of A is preferred by IUPAC, ISO and IEC.
These five common potentials are all potential energies, but there are also entropy potentials. The thermodynamic square can be used as a tool to recall and derive some of the potentials.
Just as in mechanics, where potential energy is defined as capacity to do work, similarly different potentials have different meanings like the below:
From these meanings (which actually apply in specific conditions, e.g. constant pressure, temperature, etc.), for positive changes (e.g., ΔU > 0), we can say that ΔU is the energy added to the system, ΔF is the total work done on it, ΔG is the non-mechanical work done on it, and ΔH is the sum of non-mechanical work done on the system and the heat given to it.