Аннотация:Distribution of tritium between vapor and lithium chloride aqueous solutions at 30–80 °C has been studied with the aid of vacuum distillation technique. “Positive” H/T VPIE (separation ratio increases with solute concentration) was observed. This ratio depends linearly on the salt molality and decreases with temperature. The results are in agreement with theoretical estimates of “free” water – hydrate shell H/T isotope equilibrium constants done with DFT force field calculations and harmonic oscillator quantum statistics. Found growth of the separation ratio may be practically important for developing extractive distillation process to remove tritium from technological solutions and liquid wastes of nuclear industry.