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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.
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).
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 ...
This is the most useful form of the second law of thermodynamics in chemistry, where free-energy changes can be calculated from tabulated enthalpies of formation and standard molar entropies of reactants and products. [19] [15] The chemical equilibrium condition at constant T and p without electrical work is dG = 0.
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.
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.
Equilibrium thermodynamic processes may involve fluxes but these must have ceased by the time a thermodynamic process or operation is complete bringing a system to its eventual thermodynamic state. Non-equilibrium thermodynamics allows its state variables to include non-zero fluxes, which describe transfers of mass or energy or entropy between ...
For thermodynamics, a natural process is a transfer between systems that increases the sum of their entropies, and is irreversible. [2] Natural processes may occur spontaneously upon the removal of a constraint, or upon some other thermodynamic operation , or may be triggered in a metastable or unstable system, as for example in the ...