Thermodynamic Processes and Laws

Jun 26, 2025

Overview

This lecture discusses the concepts of reversible and irreversible thermodynamic processes, providing examples and introducing the Clausius statement of the second law of thermodynamics.

Reversible and Irreversible Processes

  • A reversible process can be reversed, restoring both system and environment to their original states via the same path.
  • The quasi-static requirement means the process must proceed through a series of equilibrium states to be reversible.
  • In reality, almost all processes are irreversible, meaning the environment cannot be restored with the system.
  • Irreversible processes often occur because they are not quasi-static and involve finite gradients (e.g., temperature differences).
  • Example: Gas expanding into a vacuum is irreversible because the process is not in equilibrium at any moment.
  • On a molecular level, time-reversal is possible for single particles, but not for systems with many particles due to loss of trajectory information through collisions.
  • Probability of a macroscopic system spontaneously returning to its initial state is virtually zero, even within the age of the universe.

Second Law of Thermodynamics (Clausius Statement)

  • Clausius statement: Heat never flows spontaneously from a colder object to a hotter object.
  • "Spontaneously" means without external work or intervention.
  • The irreversibility of natural processes (like heat flow) is a consequence of the second law.

Examples and Applications

  • Spontaneous heat flow always occurs from higher to lower temperature, never the reverse.
  • Isothermal and adiabatic processes are reversible if the system remains in equilibrium throughout.
  • Other reversible processes include isobaric (constant pressure) and isochoric (constant volume) processes, under ideal conditions.
  • Real processes deviate from ideal reversible models due to practical limitations.

Key Terms & Definitions

  • Reversible Process — A process where system and environment can both be restored to their initial states by retracing the process path.
  • Irreversible Process — A process where system and environment cannot both be restored to their initial states; common in nature.
  • Quasi-Static — Describes a process proceeding infinitely slowly through equilibrium states.
  • Second Law of Thermodynamics (Clausius Statement) — Heat never flows spontaneously from a cold to a hot object.
  • Isothermal Process — Takes place at constant temperature.
  • Adiabatic Process — Occurs with no heat transfer.
  • Isobaric Process — Occurs at constant pressure.
  • Isochoric Process — Occurs at constant volume.

Action Items / Next Steps

  • Review and understand examples of reversible and irreversible processes.
  • Study the Clausius statement and other forms of the second law.
  • Prepare for next lecture on heat engines (Section 4.2).