Evidence for the presence of OH-groups in solid alkaline meta-, para-B- and ψ-metatungstates is given by infrared and 1 H-nuclear magnetic resonance spectra. The three tungstates have to be formulated as M I 6 [W 12 O 38 (OH) 2 ] • x H 2 O, M I 10 [ W 12 O 36 (OH) 10 ] • x H 2 O and M I 12 [W 24 O 72 (OH) 12 • x H 2 O respectively. The mole masses of the different polytungstates were calculated from the speed of sedimentation in the ultracentrifuge. In the concentration range covered, 10 -2 > Cwo 4 2 Ⓡ > 10 -4 , the same ions occur as in the solid state. The effect of aging and heating on polytungstate solutions was studied by means of pH-measurements, by pH-titrations, by ultraviolet spectra, and by the T-jump relaxation method. The para· tungstate-A-ion [W 6 20 (OH)] 5 ® formed upon acidification of a H®/WO 4 2 ® = 1,167 ratio solution according to the equation 6 WO 4 2 ® + 7 H® ⇄ [W 6 O 20 (OH)] 5 ® [log K ∼ 57,5] is in equilibrium with the paratungstate-B-ion [W 12 O 36 (OH) 10 ] 10® . In a solution of solid paratungstate-B the same equilibrium is attained. Upon aging and, more rapidly, by heating the para-A-/para-B-solution in equilibrium changes to -ψ-meta and finally to metatungstate. During this process an increase in the pH-value is observed due to the reduced acidity of the para-B-ion and to the enhanced condensation of para-(probably of para-B only) to ψ-meta and further to metatungstate. Upon acidification to the H®/WO 4 2® ratio Ρ=1,50 the ψ-meta-ion is formed quantitatively which changes to the metaion slowly. For P=1,50 characteristic ultraviolet absorption bands indicate the formation of a new polytungstate species [ W 12 O x (OH) y ] 72 — ( 2x+y ), called polytungstate-Y. It changes rapidly and quantitatively to ψ-meta-tungstate. In aged solutions with P ≧ 1,50 only the meta-ion is found. In solutions with Ρ < 1,50 WO 4 2e , polytungstate-X-ions were found besides meta-ions. The relative concentration of these ions as a function of Ρ is given. The so-called X-species is probably the para-B-ion. By means of a scheme, the reactions upon acidification of a monotungstate solution are illustrated.
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