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Most polyols (L = alditol or carbohydrate) form dinuclear tungstate complexes according to the over-all equilibrium 2WO4(2-) + 2H+ + L equal equilibrium [W2O7L]2- + H2O. When the reaction is fast and complete, it allows the acidimetric titration of tungstate. The formation constants of the complexes of a series of polyols were determined by potentiometry. Their values were higher at low ionic strengths. Opposite structural factors govern the stabilities and the formation rates of complexes: alditols of threo configuration react with tungstate faster than those of erythro configuration, but the stability order is erythro greater than threo. Of the polyols investigated, only xylitol and D-glucitol (sorbitol) allowed a fast and accurate potentiometric titration. Using 0.02 M HCl as titrand, 0.04 mmol of tungstate was determined in a volume of 100 cm3. The interference of molybdate is discussed in detail.