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[a] While processes in isolated systems are never reversible, [3] cyclical processes can be reversible or irreversible. [4] Reversible processes are hypothetical or idealized but central to the second law of thermodynamics. [3] Melting or freezing of ice in water is an example of a realistic process that is nearly reversible.
An irreversible process increases the total entropy of the system and its surroundings. The second law of thermodynamics can be used to determine whether a hypothetical process is reversible or not. Intuitively, a process is reversible if there is no dissipation. For example, Joule expansion is irreversible because initially the system is not ...
For reversible processes, an isentropic transformation is carried out by thermally "insulating" the system from its surroundings. Temperature is the thermodynamic conjugate variable to entropy, thus the conjugate process would be an isothermal process , in which the system is thermally "connected" to a constant-temperature heat bath.
The equality holds in the reversible case [70] and the strict inequality holds in the irreversible case, with T surr as the temperature of the heat bath (surroundings) here. The reversible case is used to introduce the state function entropy. This is because in cyclic processes the variation of a state function is zero from state functionality.
The first established thermodynamic principle, which eventually became the second law of thermodynamics, was formulated by Sadi Carnot in 1824 in his book Reflections on the Motive Power of Fire. By 1860, as formalized in the works of scientists such as Rudolf Clausius and William Thomson , what are now known as the first and second laws were ...
It is thereby radically different from a fictive quasi-static 'process' that proceeds infinitely slowly throughout its course, and is fictively 'reversible'. Classical thermodynamics allows that even though a process may take a very long time to settle to thermodynamic equilibrium, if the main part of its course is at a finite rate, then it is ...
If at every point in the cycle the system is in thermodynamic equilibrium, the cycle is reversible. Whether carried out reversible or irreversibly, the net entropy change of the system is zero, as entropy is a state function. During a closed cycle, the system returns to its original thermodynamic state of temperature and pressure.
A and B can react to form C and D or, in the reverse reaction, C and D can react to form A and B. This is distinct from a reversible process in thermodynamics. Weak acids and bases undergo reversible reactions. For example, carbonic acid: H 2 CO 3 (l) + H 2 O (l) ⇌ HCO 3 − (aq) + H 3 O + (aq).