Chemistry

Phase equilibria and diagrams

Gibbs phase rule, unary diagrams, eutectics, and the lever rule.

Basics

Phase rule

Gibbs’s phase rule is F = C − P + 2. F is degrees of freedom, C independent components, P phases. For one-component water the triple point has F=0 so T and P are fixed. In binaries people often hold pressure fixed and write F = C − P + 1. Lines and regions on a diagram make those counts visible. This is a class sketch; non-ideal systems need activities.

Unary phase diagram

On a P–T diagram for water or CO₂, curves are where two phases coexist. Beyond the critical point sits a supercritical fluid with no liquid–gas distinction. Water’s melting curve sloping left means higher pressure lowers the melting point. Sublimation is solid to gas without a liquid. Labels differ by substance.

Binary eutectic

When two components barely mix as solids, a eutectic appears: liquid plus two solids coexist at that composition and temperature. Above the liquidus everything is liquid; between liquidus and solidus, liquid plus solid; below the solidus, solid. Lead–tin solder is the textbook case. A flat hold on a cooling curve flags the eutectic.

Lever rule

In a two-phase field, where bulk composition sits between the two phases sets the phase fractions. The longer arm is the lesser phase — mass balance drawn like a seesaw. Stay consistent with mole or mass fraction on the axis. Apply it only on a tie line (isotherm).

Formulas

Gibbs phase rule

F = C − P + 2

Condensed systems at fixed P often use +1.

Symbols

  • F degrees of freedom
  • C number of components
  • P number of phases

Clausius–Clapeyron (sketch)

dP/dT = ΔH / (T ΔV)

Slope of a coexistence curve. For vapor, ΔV≈V_gas.

Symbols

  • ΔH enthalpy of transition
  • ΔV volume change

Lever rule

f_α = (w_β − w) / (w_β − w_α)

Bulk w and phase compositions w_α, w_β. Mass-fraction example.

Symbols

  • f_α fraction of phase α
  • w overall composition

Key table

Water triple point 273.16 K, 611.657 Pa — an anchor of the temperature scale
Critical point (water) about 647 K, 22.1 MPa
Eutectic solder Sn–Pb eutectic freezes all at once near 183 °C

In this field