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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 ...
[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).
For any irreversible process, since entropy is a state function, we can always connect the initial and terminal states with an imaginary reversible process and integrating on that path to calculate the difference in entropy. Now reverse the reversible process and combine it with the said irreversible process.
In thermodynamics, the Gibbs free energy or Helmholtz free energy is essentially the energy of a chemical reaction "free" or available to do external work. Historically, the "free energy" is a more advanced and accurate replacement for the thermochemistry term “affinity” used by chemists of olden days to describe the “force” that caused chemical reactions.
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 condensation ...
An irreversible process degrades the performance of a thermodynamic system, designed to do work or produce cooling, and results in entropy production. The entropy generation during a reversible process is zero. Thus entropy production is a measure of the irreversibility and may be used to compare engineering processes and machines.
In some cases, when analyzing a thermodynamic process, one can assume that each intermediate state in the process is at equilibrium. Such a process is called quasistatic. [4] For a process to be reversible, each step in the process must be reversible. For a step in a process to be reversible, the system must be in equilibrium throughout the step.