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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 ...
and thus for a system kept at constant temperature and volume and not capable of performing electrical or other non-PV work, the total free energy during a spontaneous change can only decrease. This result seems to contradict the equation d F = − S d T − P d V , as keeping T and V constant seems to imply d F = 0, and hence F = constant.
These include the Boltzmann constant, which gives the correspondence of the dimension temperature to the dimension of energy per degree of freedom, and the Avogadro constant, which gives the correspondence of the dimension of amount of substance with the dimension of count of entities (the latter formally regarded in the SI as being dimensionless).
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 ...
For a process at constant temperature and pressure without non-PV work, this inequality transforms into <. Similarly, for a process at constant temperature and volume, <. Thus, a negative value of the change in free energy is a necessary condition for a process to be spontaneous; this is the most useful form of the second law of thermodynamics ...
The generalized force, X, corresponding to the external variable x is defined such that is the work performed by the system if x is increased by an amount dx. For example, if x is the volume, then X is the pressure. The generalized force for a system known to be in energy eigenstate is given by:
One such potential is the Helmholtz free energy (A), for a closed system at constant volume and temperature (controlled by a heat bath): = Another potential, the Gibbs free energy (G), is minimized at thermodynamic equilibrium in a closed system at constant temperature and pressure, both controlled by the surroundings:
The third law of thermodynamics states: As the temperature of a system approaches absolute zero, all processes cease and the entropy of the system approaches a minimum value. This law of thermodynamics is a statistical law of nature regarding entropy and the impossibility of reaching absolute zero of temperature. This law provides an absolute ...