Kinetics of the oxidation of octacyanomolybdate(IV) by periodate in aqueous acid

Summary The kinetics of oxidation of [Mo(CN)₈]^4– by IO ₄ ^– in aqueous acid is described by the equation: d[{Mo(CN)₈}^3–]/ dt=2k₃[{Mo(CN)₈}^4–][IO ₄ ^– ][H⁺]. Unlike IO ₄ ^– oxidations of [Fe(CN)₆]^4– and [W(CN)₈]^4–, no [H⁺] independent term exists in the [Mo(CN)₈]^4– reaction, which indicates that, in neutral and alkaline solutions, oxidation of [Mo(CN)₈]^4– is thermodynamically unfavourable. An inner-sphere mechanism, consistent with the rate law, is proposed. This conclusion is based, in the absence of direct evidence, on the observed behaviour of IO ₄ ^– as an inner-sphere oxidant.     

Coulometric determination of ascorbic acid with electrogenerated octacyanomolybdate(V)

A coulometric-potentiometric method is described for the estimation of ascorbic acid with octacyanomolybdate(V) generated electrolytically. The accuracy and precision are comparable with those of the other coulometric methods available.     

Kinetics of oxidation of octacyanomolybdate(V) ion by thiosulfate

The oxidation of thiosulfate by octacyanomolybdate(V) in the pH range of 4,0 to 5,1 is catalyzed by alkali metal ions and shows first order dependence on the concentrations of thiosulfate, octacyanomolybdate(V) and alkali metal ions and is independent of the hydrogen ion concentration. A mechanism for the reaction is proposed.

---

(V) pH=4,0–5,1 . , (V) . . .

     

Catalytic and direct oxidation of cysteine by octacyanomolybdate(V)

The oxidation of cysteine by [Mo(CN)(8)](3-) in deoxygenated aqueous solution at a moderate pH is strongly catalyzed by Cu(2+), to the degree that impurity levels of Cu(2+) are sufficient to dominate the reaction. Dipicolinic acid (dipic) is a very effective inhibitor of this catalysis, such that with 1 mM dipic, the direct oxidation can be studied. UV-vis spectra and electrochemistry show that [Mo(CN)(8)](4-) is the Mo-containing product. Cystine and cysteinesulfinate are the predominant cysteine oxidation products. The stoichiometric ratio (Deltan(Mo(V))/Deltan(cysteine)) of 1.4 at pH 10.8 is consistent with this product distribution. At pH 1.5, the reaction is quite slow and yields intractable kinetics. At pH 4.5, the rates are much faster and deviate only slightly from pseudo-first-order behavior. With 2 mM PBN (N-phenyl-tert-butyl nitrone) present at pH 4.5, the reaction rate is about 20% less and shows excellent pseudo-first-order behavior, but the stoichiometric ratio is not significantly changed. The rates also display a significant specific cation effect. In the presence of spin-trap PBN, the kinetics were studied over the pH range 3.48-12.28, with [Na(+)] maintained at 0.09-0.10 M. The rate law is -d[Mo(V)]/dt = k[cysteine](tot)[Mo(V)], with k = {2(k(b)K(a1)K(a2)[H(+)] + k(c)K(a1)K(a2)K(a3))}/([H(+)](3) + K(a1)[H(+)](2) + K(a1)K(a2)[H(+)] + K(a1)K(a2)K(a3)), where K(a1), K(a2), and K(a3) are the successive acid dissociation constants of HSCH(2)CH(NH(3)(+))CO(2)H. Least-squares fitting yields k(b) = (7.1 +/- 0.4) x 10(4) M(-1) s(-1) and k(c) = (2.3 +/-0.2) x 10(4) M(-1) s(-1) at mu = 0.1 M (NaCF(3)SO(3)) and 25 degrees C. A mechanism is inferred in which k(b) and k(c) correspond to electron transfer to Mo(V) from the thiolate forms of anionic and dianionic cysteine.     

Reactions of octacyanomolybdate(V) and octacyanotungstate(V) with s(2) metal-ion reducing centers

The s(2) centers, Sn(II), Ge(II), and In(i) reduce Mo(V)(CN)(8)(3-) and W(V)(CN)(8)(3-) quantitatively to the corresponding octacyanomolybdate(IV) and -tungstate(iv) anions. Reductions by In(i) proceed 10(3)-10(5) times as rapidly as those by Sn(II) and Ge(II). All reactions are triggered by a single electron oxidation, yielding a much more reactive s(1) intermediate. Reductions by Sn(II) in chloride medium proceed predominantly through the SnCl(3)(-) anion. The Ge(II)-W(CN)(8)(3-) reaction is initiated by a slow unimolecular heterolysis of the Ge(II) center, yielding very nearly linear profiles when the reductant is in excess.     

Determination of hexacyanoferrate(II) with electrolytically generated octacyanomolybdate(V)

The determination of hexacyanoferrate(II) with electrolytically generated octacyanomolybdate(V) at a platinum anode over a wide pH range is described. From 1 to 20 muequiv are determined with a relative standard deviation of 0.3%.     

Kinetics and salt effects of the reduction of octacyanomolybdate(V) and octacyanotungstate(V) by sulphite ions

The kinetics of the reduction of octacyanomolybdate(V) and octacyanotungstate(V) by sulphite ions has been studied over a wide pH range. The reaction is catalysed by alkali metal ions. The rate law is found to be of the form:

The third order rate constants at [OH^?] = 0.05 mol dm^?3 for the reduction of Mo(CN)₈^3? and W(CN)^3?₈ were determined as 6.2 x 10³dm⁶mol^?2 s^?1 and 22.3 dm⁶mol^?2s^?1 respectively at 298 K for A⁺ = Na⁺ while K_a for the hydrogen sulphite ion was determined as 2.4 x 10^?8 mol dm^?3. It was established that the reaction proceeds via an outer-sphere mechanism. An explanation for the alkali metal ion catalysis is proposed.     

Reduction of silver(II) oxide by the solvent in acid media

The reaction of silver(II) oxide with water to yield silver(I) ions and oxygen is an important side-reaction in procedures which use silver(II) oxide as the oxidant. This reaction has been examined in solutions which were 0.01-1M in respect to sulphuric or perchloric acid. The rate of reduction varied directly with the amount of solid added and was a complex function of the concentrations of hydrogen ions, silver(I) ions and anions present. The kinetic results have been used to postulate a mechanism for the reaction.     

Motion of cations and phase situation in solid tetrabutylammonium octacyanomolybdate(V)

Summary Studies of the i.r. spectra, lattice parameters and the proton second moment in [n-Bu₄N]₃[Mo(CN)₈] over the 77K to 383 K region are reported.¹Hn.m.r. data provide evidence for different rotational processes which are discussed in some detail. Atca. 260 K and 295 K the compound exibits anomalous changes in i.r. spectra and lattice parameters. The results reveal the existence of polymorphism in solid tetrabutylammonium octacyanomolybdate(V).     

A kinetic study of the oxidation of thiourea by octacyanomolybdate(V) and octacyanotungstate(V) ions in an alkaline medium

The kinetics of the oxidation of thiourea to sulfate by octacyanomolybdate(V) and octacyanotungstate(V) ions have been studied in an alkaline medium. The reactions are first order with respect to thiourea, octacyanomolybdate(V) or octacyanotungstate(V), hydroxide and sodium ions. The observed fourth order rate constants are ca. 1.20×10⁷ and ca. 9.80×10³ M^–3 min^–1 for oxidation by Mo(CN) ₈ ^3– and W(CN) ₈ ^3– , respectively at 298K. A reaction mechanism is proposed.

---

(V) (V) . , (V) (V), . 1,2·10⁷ 9,8·10³ M^{–3 –1} Mo(CN)₈ ^–3 W(CN)₈ ^–3 298 . .

     

Coulometric determination of Ce(III) in alkaline solutions with electrogeneated octacyanomolybdate(V)

The coulometric determination of Ce(III) with octacyanomolybdate(V) in concentrated carbonate-bicarbonate buffer solutions was carried out. The current efficiency for electrogeneration of octacyanomolybdate(V) and the optimum conditions for analytical determinations of microquantities of cerium have been investigated.     

Reduction of hexachloroiridate (IV) by benzene-1,2-diol in aqueous perchloric acid

The kinetics of the reaction between benzene-1,2-diol(catechol) and hexachloroiridate (IV) have been measured in aqueous acidic perchlorate solutions by the stopped-flow method. The reaction is second order overall, and first order in each reactant. A reverse reaction also occurs, but it is much slower than the forward process. Observed rate constants are dependent on acidity, but the variation can be attributed to activity rather than mechanistic effects. The reaction appears to proceed predominantly by an outer sphere electron transfer mechanism, yielding o-benzoquinone and hexachloroiridate (III), although monoaquopentachloroiridate (III) is formed also at the higher [catechol]/[IrCl₆^2?]ratios.     

Oxidation of thiourea and thioacetamide by octacyanomolybdate(v) anion in perchloric acid

Summary The kinetics of the reduction of octacyanomolybdate(V) anion by thiourea and thioacetamide have been studied in aqueous HClO₄ at constant ionic strengthI=0.10 mol dm^–3 (NaClO₄). The rate of oxidation of these substrates by the oxidant shows a first order dependence in both the oxidant and the substrates and while the thiourea system exhibits an inverse first-order dependence on [H⁺] that of thioacetamide is found to be first-order in [H⁺]. The variation observed in [H⁺] dependences in these reactions is attributed to the nature of the thiourea in the pH range used in this study and the inductive effect of the methyl group in thioacetamide. A mechanistic interpretation of these observations is advanced.     

Kinetics of peroxodisulphate oxidation of octacyanomolybdate(IV) in concentrated aqueous salt solutions

Summary Rate constants are reported for the oxidation by peroxodisulphate ions of octacyanomolybdate(IV) in concentrated aqueous salt solutions containing up to 6 mol dm^–3 salt including mixed salt solutions. The dependence of the logarthm of rate constant on salt concentration is discussed in terms of ionic hydration enthalpies and B-viscosity coefficients. The analysis confirms that ion-pairs play a key role in determining reactivities in these systems.     

Synthesis of omega-(hetero)arylalkynylated alpha-amino acid by Sonogashira-type reactions in aqueous media

Mild conditions are described that allow the palladium-catalyzed cross-coupling of C(alpha)-alkynylated glycine with a wide variety of electron-rich and electron-poor aryl and heteroaryl halides in aqueous media.     

Kinetics and mechanism of oxidation of formic acid by bismuth(V) in aqueous phosphoric acid medium

The solution of bismuth(V) was prepared by digesting sodium bismuthate in aqueous phosphoric acid (3.0 mol dm⁻³), the resulting pink colour solution absorbs in the visible region at 530 nm (640 dm³ mol⁻¹ cm⁻¹). The stoichiometry of the oxidation of formic acid by bismuth(V) corresponds to the reaction as represented by the Eq. ( 1 ). (1) The observed kinetic rate law is given by the Eq. ( 2 ); (2) where Bi^V and [HCO₂H] are the gross analytical concentrations of bismuth(V) and formic acid respectively. A plausible reaction mechanism corresponding to the rate law (2) has been proposed. Also the pattern of reactivity of bismuth(V) in HCIOHF mixture and H₃PO₄ respectively has been compared. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 491–497, 2000     

Polyisobutylene-block-poly(methacrylic acid) diblock copolymers: self-assembly in aqueous media

Ionic amphiphilic diblock copolymer polyisobutylene-block-poly(methacrylic acid) (PIBx-b-PMAAy), with various lengths of nonpolar (x=25-75) and polyelectrolyte (y=170-2600) blocks, spontaneously dissolve in aqueous media at pH>4, generating macromolecular assemblies, the aggregation number of which depends on external stimuli (pH and ionic strength). Spherical micellar morphology with a compact core formed by the PIB blocks and a swollen corona built up from the PMAA blocks was deduced by cryogenic transmission electron microscopy. The micelles were further characterized by means of dynamic and static light scattering as well as small-angle neutron scattering. The critical micellization concentration, estimated by means of fluorescence spectroscopy with the use of pyrene as a polarity probe, is decisively determined by the length of the PIB block and is insensitive to changes in the length of the PMAA block.