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New observations regarding deterministic, time-reversible thermostats and Gauss's principle of least constraint

Joanne N Bright1, Denis J Evans, Debra J Searles

  • 1Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 0200, Australia.

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Zeroth Law of Thermodynamics01:14

Zeroth Law of Thermodynamics

Experimentally, if object A is in equilibrium with object B, and object B is in equilibrium with object C, then object A is in equilibrium with object C. That statement of transitivity is called the "zeroth law of thermodynamics." For example, a cold metal block and a hot metal block are both placed on a metal plate at room temperature. Eventually, the cold block and the plate will be in thermal equilibrium. In addition, the hot block and the plate will be in thermal equilibrium. By the zeroth...
Entropy01:18

Entropy

The first law of thermodynamics is quantitatively formulated via an equation relating the internal energy of a system, the heat exchanged by it, and the work done on it. A quantitative formulation of the second law of thermodynamics leads to defining a state function, the entropy.
When an ideal gas expands isothermally, the disorder in the gas increases. From the molecular perspective, the gas molecules have more volume to move around in.
Consider an infinitesimal step in the expansion, which...
Entropy02:39

Entropy

Salt particles that have dissolved in water never spontaneously come back together in solution to reform solid particles. Moreover, a gas that has expanded in a vacuum remains dispersed and never spontaneously reassembles. The unidirectional nature of these phenomena is the result of a thermodynamic state function called entropy (S). Entropy is the measure of the extent to which the energy is dispersed throughout a system, or in other words, it is proportional to the degree of disorder of a...
Statements of the Second Law of Thermodynamics01:15

Statements of the Second Law of Thermodynamics

The second law of thermodynamics can be stated in several different ways, and all of them can be shown to imply the others. The Clausius’ statement of the second law of thermodynamics is based on the irreversibility of spontaneous heat flow. It states that heat will not flow from the colder body to the hotter body unless some other process is involved. Additionally, as per the Kelvin’s statement, it is impossible to convert the heat from a single source into work without any other effect. This...
Limits of the First Law of Thermodynamics01:22

Limits of the First Law of Thermodynamics

Spontaneous processes, like a rock falling to the ground or sodium reacting with chlorine, occur without external work and often involve a decrease in the system‘s energy. However, certain endothermic processes, such as the dissolution of sodium chloride in water, occur spontaneously even though they increase the energy of the system. This limitation suggests that the First Law of Thermodynamics, which states that the total energy of a system is constant in an isolated system, cannot fully...
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Reversible and Irreversible Processes

The thermodynamic processes can be classified into reversible and irreversible processes. The processes that can be restored to their initial state are called reversible processes. It is only possible if the process is in quasi-static equilibrium, i.e., it takes place in infinitesimally small steps, and the system remains at equilibrium However, these are ideal processes and do not occur naturally. An ideal system undergoing a reversible process is always in thermodynamic equilibrium within...