is the total system pressure, Kp is the equilibrium constant expressed in terms of partial pressures and KX is the equilibrium constant expressed in terms of mole fractions. The above change in composition is in accordance with Le Chatelier's principle and does not involve any change of the equilibrium constant with the total system pressure. Indeed, for ideal-gas reactions Kp is independent of pressure. In a condensed phase, the pressure dependence of the equilibrium constant is associated with the reaction volume. For reaction: α A + β B σ S + τ T the reaction volume is: where V̄ denotes a partial molar volume of a reactant or a product. For the above reaction, one can expect the change of the reaction equilibrium constant (based either on mole-fraction or molal-concentration scale) with pressure at constant temperature to be: The matter is complicated as partial molar volume is itself dependent on pressure. Effect of isotopic substitution Isotopic substitution can lead to changes in the values of equilibrium constants, especially if hydrogen is replaced by deuterium (or tritium). This equilibrium isotope effect is analogous to the kinetic isotope effect on rate constants, and is primarily due to the change in zero-point vibrational energy of H–X bonds due to the change in mass upon isotopic substitution. The zero-point energy is inversely proportional to the square root of the mass of the vibrating hydrogen atom, and will therefore be smaller for a D–X bond that for an H–X bond. An example is a hydrogen atom abstraction reaction R' + H–R R'–H + R with equilibrium constant KH, where R' and R are organic radicals such that R' forms a stronger bond to hydrogen than does R. The decrease in zero-point energy due to deuterium substitution will then be more important for R'–H than for R–H, and R'–D will be stabilized more than R–D, so that the equilibrium constant KD for R' + D–R R'–D + R is greater than KH. This is summarized in the rule the heavier atom favors the stronger bond. Similar effects occur in solution for acid dissociation constants (Ka) which describe the transfer of H+ or D+ from a weak aqueous acid to a solvent molecule: HA + H2O = H3O+ + A− or DA + D2O D3O+ + A−. The deuterated acid is studied in heavy water, since if it were dissolved in ordinary water the deuterium would rapidly