of vaporization or condensation to the rate of change of vapor pressure with temperature or, in the case of a solid-liquid transformation, it relates the latent heat of fusion or solidification to the rate of change of melting point with pressure DERIVATION Imagine a piston containing a vapor in equilibrium with its liquid. Thus, A (l) A (g) If the piston to be pulled out, at constant temperature; liquid evaporates and the pressure remains constant. If the piston is pushed in, vapor condenses, at constant temperature and pressure. DERIVATION During this process, the Gibbs free energy (G) of the system remains constant. In the equilibrium system, G = H - TS where H is the latent heat of vaporization, T the temperature and S the entropy of the system Since G of the said system remains constant, G 2 G 1 = G = H - TS = 0 Thus, H = TS DERIVATION However, for gases, H = U + PV, where U is the internal energy of the system, making the previous equation H =TS = U + PV Given two states in the compression, the changes in entropy (S), internal energy (U) and volume (V) would become constant. DERIVATION Differentiating both sides with respect to temperature, we get S = V dP dT dP dT S V S 2 S 1 V 2 V 1 = = DERIVATION However, the change in entropy S is given by S = L / T where L is the latent heat of vaporization Thus, we arrive at the Clausius Clapeyron equation dP dT S V L T (V 2 V 1 ) = = DERIVATION When the transition is to a gas phase, the final volume can be many times the size of the initial volume and thus V can be approximated as V 2 . Furthermore, at low pressures, the gas phase may be approximated by the ideal gas law PV = nRT, changing the previous equation to: dP dT S V LP nRT 2 = = DERIVATION Since H vap = L / n, Also since H vap is independent of pressure and temperature and R is a constant, integrating both sides, we get dP P dT H vap T 2 R = ln P 1 H vap T R = + C DERIVATION If the vapor pressure was measured at two separate temperatures, we have two points on the same line. Subtracting these two, we get ln P 1 1 H vap T 1 R = + C ln P 2 1 H vap T 2 R = + C ln P 2 - ln P 1 H vap R = ( 1 T 2 1 T 1 ) DERIVATION Finally, we get the more commonly known form of the Clausius Clapeyron equation ln H vap R = ( 1 T 2 1 T 1 ) P 2 P 1