Equilibrium Studies of Polyanions. I. Isopolyvanadates in Acidic Media.

Rossotti, F. J. C.; Rossotti, Hazel; Ormerod, John G.; Stenhagen, Einar; Thorell, B.

doi:10.3891/acta.chem.scand.10-0957

Cited by 146 publications

(36 citation statements)

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“…The resonance is accordingly assigned t o the vanadyl ion, V02f. Vanadyl sulfates are known stable salts and are obtained fro111 strongly acid solutions (12). I t is evident from these results that a considerable ainount of chenlical information is derivable from nuclear resonances of complex ions.…”

Section: (B) Oxy-ions O J T H N a D I~~n Zmentioning

confidence: 89%

Nuclear Magnetic Resonance Investigations of Some Group v Metal Fluorides and Oxyions

Hatton¹,

Saitō²,

Schneider³

1965

Can. J. Chem.

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The nuclear magnetic resonances of 51V, g3Nb, lZ1Sb, lZ3Sb, and lS'Ta in solutions of the pentafluorides of these elements were measured. All of these nuclei have large electric quadrupole moments. I n most cases the chemical species observed was identified by spin-multiplet splitting of the metal resonance. In aqueous 48% H F solutions the lBlTa resonance could not be observed; the 12'Sb and lZ3Sb resonances consist of a symmetrical septet, corresponding t o the hexafluoride ion; the g3Nb resonance consists of a single exchange narrowed line; and the 51V resonance co~lsists of a symmetrical quintet, corresponding to the VOF4-ion. In alcohol solution NbF5 disproportionates to form NbF6-, whereas in ether and triethylamine solutions, the complexes NbF5.OEtz and NbF5.NEta are formed. The latter complexes were confirmed by proton resonance measurements. Resonances of 51V in aqueous solutions of V205 and of IU'H4V03 as a function of pH show a parallel behavior and reveal the presence of six different oxyions of vanadium. Five of these resonances are assigned to the species, V043-, VO3-, V 2 0~~-, V3010~-and V02+, on the basis of the resonance line width and the p H range in which the resonance appears.

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Section: (B) Oxy-ions O J T H N a D I~~n Zmentioning

confidence: 89%

Nuclear Magnetic Resonance Investigations of Some Group v Metal Fluorides and Oxyions

Hatton¹,

Saitō²,

Schneider³

1965

Can. J. Chem.

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“…The rate law (4) indicates that the plot of kl/[H+] versus [H+] should be linear with a positive intercept on the kl/[H+] axis. However, such a plot again showed a break near about 2M perchloric acid.…”

Section: Resultsmentioning

confidence: 99%

Mechanism of oxidation of cyclohexanehexol (inositol) by quinquevalent vanadium

Kumar

Mehrotra

1974

Int J of Chemical Kinetics

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The oxidation of inositol by quinquevalent vandadium in acid medium is a first-order reaction both in vanadium (V) and inositol. The stoichiometry of the reaction is consistent with the use of two equivalents of vanadium (V) per mole of inositol with the formation of one more of inosose. The reaction is catalyzed both by sulfuric and perchloric acid, but the rate is faster in sulfuric acid than in perchloric acid. In 1M-6M perchloric acid solutions the reaction has shown a variable order in H' , but in solutions of 2M-5M sulfuric and perchloric acid of constant ionic strength, the rate has a linear dependence on [H+I2. There is also a linear correlation between the rate and bisulfate ions in sulfuric acid at constant hydrogen ion concentration. The energy of activation is found to be 19 kcal/mole and a negative entropy value of -14 e.u. A suitable mechanism, consistent with the kinetics in 2M-5M acid solutions, is suggested and the values of various rate constants are evaluated.

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“…It was proposed (Dyrssen, 1952) j = -440 mV L mol -1 for 0.100 mol L -1 NaClO 4 , while it was found that j = -16.5 and -63 mV L mol -1 for 3.00 and 1.00 mol L -1 NaClO 4 , respectively (Rossotti et al, 1956). …”

Section: Resultsmentioning

confidence: 99%