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The internal energy depends only on the internal state of the system and not on the particular choice from many possible processes by which energy may pass into or out of the system. It is a state variable, a thermodynamic potential, and an extensive property. [5] Thermodynamics defines internal energy macroscopically, for the body as a whole.
It is defined only up to an arbitrary additive constant of integration, which can be adjusted to give arbitrary reference zero levels. This non-uniqueness is in keeping with the abstract mathematical nature of the internal energy. The internal energy is customarily stated relative to a conventionally chosen standard reference state of the system.
The concept of internal energy and its relationship to temperature. If a system has a definite temperature, then its total energy has three distinguishable components, termed kinetic energy (energy due to the motion of the system as a whole), potential energy (energy resulting from an externally imposed force field), and internal energy. The ...
The generalized force for a system known to be in energy eigenstate is given by: X = − d E r d x {\displaystyle X=-{\frac {dE_{r}}{dx}}} Since the system can be in any energy eigenstate within an interval of δ E {\displaystyle \delta E} , we define the generalized force for the system as the expectation value of the above expression:
The principle of minimum energy is essentially a restatement of the second law of thermodynamics. It states that for a closed system, with constant external parameters and entropy, the internal energy will decrease and approach a minimum value at equilibrium. External parameters generally means the volume, but may include other parameters which ...
The remaining variable, as well as other quantities such as the internal energy and the entropy, would be expressed as state functions of these three variables. The state functions satisfy certain universal constraints, expressed in the laws of thermodynamics , and they depend on the peculiarities of the materials that compose the concrete system.
Since the total change in entropy must always be larger or equal to zero, we obtain the inequality W ≤ − Δ F . {\displaystyle W\leq -\Delta F.} We see that the total amount of work that can be extracted in an isothermal process is limited by the free-energy decrease, and that increasing the free energy in a reversible process requires work ...
An example of a system that does not have a unique ground state is one whose net spin is a half-integer, for which time-reversal symmetry gives two degenerate ground states. For such systems, the entropy at zero temperature is at least k B ln(2) (which is negligible on a macroscopic scale).