Change in Entropy of System and Surroundings

Jul 6, 2025

Overview

This lecture discusses how entropy and enthalpy influence whether a process, like water freezing, is spontaneous, and examines the roles of the system and surroundings.

Entropy Changes in Freezing Water

  • Freezing water is a phase change from liquid to solid.
  • During freezing, entropy (ΔS) of the water (system) decreases (ΔS < 0).
  • According to the second law of thermodynamics, total entropy of the universe must increase for a process to be spontaneous.
  • The system (water) is only a part of the universe; the surroundings must also be considered.

System and Surroundings

  • The universe is divided into the system (the reaction or process) and the surroundings (everything else).
  • Change in entropy for the universe: ΔS_univ = ΔS_sys + ΔS_surr.
  • For freezing to be spontaneous, the increase in entropy of the surroundings must outweigh the decrease in entropy of the system.

Role of Enthalpy (ΔH)

  • Freezing water has a negative enthalpy change (ΔH_sys < 0); this is an exothermic process.
  • Exothermic means heat is released from the system to the surroundings.
  • Released heat increases the temperature of the surroundings (ΔT_surr > 0).
  • As temperature of the surroundings increases, their entropy (ΔS_surr) also increases.

Entropy of the Surroundings

  • The increase in entropy of the surroundings (ΔS_surr > 0) is due to heat transfer from the exothermic process.
  • If ΔS_surr is large enough, it makes ΔS_univ positive, allowing the process to be spontaneous.
  • If the process were endothermic (ΔH_sys > 0), heat would be absorbed from the surroundings, decreasing ΔS_surr.

Key Terms & Definitions

  • Entropy (ΔS) — A measure of disorder or randomness in a system.
  • Enthalpy (ΔH) — Heat content of a system at constant pressure.
  • Exothermic — A process that releases heat to the surroundings (ΔH < 0).
  • Endothermic — A process that absorbs heat from the surroundings (ΔH > 0).
  • System — The part of the universe being studied (e.g., freezing water).
  • Surroundings — Everything outside the system.

Action Items / Next Steps

  • Review examples of spontaneous and non-spontaneous processes using entropy and enthalpy.
  • Practice calculating ΔS_univ for given reactions.