The partitioning of Gd in the experimental system diopside-aqueous vapor as a function of temperature, pressure, composition of the phases, time, grain size, solid-liquid ratio and Gd concentration has been investigated. A radioactive tracer measurement was used to determine Gd concentration in the separated phases. Diposides were reacted with aqueous vapor containing tracer Gd and reversibility was tested by reacting Gd-doped diopsides with pure aqueous vapor. Equilibration of Gd between the bulk of the diopside and the liquid was found to be limited by the slow rate of Gd diffusion in diopside, maximum value of D = 2 × 10⁻¹⁵cm²sec⁻¹ at 800°C and 1 kb. Depending on whether the diopside was previously synthesized or synthesized from an oxide mix during the experiment, Gd concentrations were zoned in the crystal such that higher concentrations existed at the edges or center, respectively. Equilibrium is difficult to achieve in these experiments, but at the optimum experimental conditions for equilibration, the Gd diopside-aqueous vapor distribution coefficient is 20 ± 6 (800°C, 1 kb) in approximate agreement with previous results of 55 ± 23. Changing the composition of the aqueous vapor indicated that possible mechanisms for Gd substitution included coupling of Gd³⁺ with H⁺ or Na⁺ replacing 2Ca²⁺, or substitution of 2Gd³⁺ for 3Ca²⁺ with formation of a cation vacancy.