PubMed · 1069508
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S Gauvain, A Pittom. 1976. Governmental action in Britain.. https://doi.org/10.1111/j.1749-6632.1976.tb23115.x
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The oxidation of D-lactobionic acid by Cr(VI) yields the 2-ketoaldobionic acid and Cr(3+) as final products when a 20-times or higher excess of the aldobionic acid over Cr(VI) is used. The redox reaction takes place through a complex multistep mechanism, which involves the formation of intermediate Cr(IV) and Cr(V) species. Cr(IV) reacts with lactobionic acid much faster than Cr(V) and Cr(VI) do, and cannot be directly detected. However, the formation of CrO(2)(2+), observed by the first time for an acid saccharide/Cr(VI) system, provides indirect evidence for the intermediacy of Cr(IV) in the reaction path. Cr(VI) and the intermediate Cr(V) react with lactobionic acid at comparable rates, being the complete rate laws for the Cr(VI) and Cr(V) consumption expressed by: -d[Cr(VI)]/dt=[k(I)+k(II)[H(+)]][lactobionicacid][Cr(VI)], where k(I)=(4.1+/-0.1) x 10(-3) M(-1) s(-1) and k(II)=(2.1+/-0.1) x 10(-2) M(-2) s(-1); and -d[Cr(V)]/dt=[k(III)[H(+)]+(k(IV)+k(V)[H(+)])[lactobionicacid]] [Cr(V)], where k(III)=(1.8+/-0.1) x 10(-3) M(-1) s(-1), k(IV)=(1.1+/-0.1) x 10(-2) M(-1) s(-1) and k(V)=(1.0+/-0.1) x 10(-2) M(-2) s(-1), at 33 degrees C. The Electron Paramagnetic Resonance (EPR) spectra show that five-co-ordinate oxo-Cr(V) bischelates are formed at pH 1-5 with the aldobionic acid bound to Cr(V) through the alpha-hydroxyacid group.
A procedure was worked out to obtain highly dispersed green silicate and oxide pigments precipitated from postgalvanic waste. The highly dispersed chromium(III) silicates and oxides were produced from the waste, originating from chromium plating, by reduction of Cr(VI) to Cr(III) employing various reducing agents. All the reductions were conducted in an acidic medium. Solutions of Cr(III), obtained in reducing processes, were employed to precipitate silicate pigments (using sodium metasilicate solution and containing mainly chromium(III) silicates) and oxide pigments (using sodium hydroxide and containing chromium(III) oxides). The precipitated silicates and oxides were subjected to a comprehensive physicochemical analysis (estimating bulk density, capacities to absorb water, dibutyl phthalate, paraffin oil, particle size distribution, and morphology of particle surface). Precipitation process (its parameters) and heating of the reactive mixture exerts a significant effect on the principal physicochemical properties of the pigments. The heating significantly affects first of all color shade of the obtained silicate and oxide pigments as well as their dispersion. Coprecipitated chromium(III) and iron(III) silicates exhibit a brownish color and a reasonably uniform character. Apart from primary agglomerates (in the range of 414-717 nm), they contain small amounts of secondary agglomerates (in the range of 4154-6445 nm). Best physicochemical parameters have been demonstrated by chromium pigments which have been precipitated from chromium solutions reduced using hydrogen peroxide. Chromium(III) oxides deserve particular distinction since their structure includes primary particles, primary agglomerates but is completely free of secondary agglomerates. The pigments manifest a brightly green color and a low capacity to absorb water (100 cm3 x 100 g(-1)). Application of hydrophobicity-inducing agents in the course of precipitation has corrected physicochemical parameters of both the oxides and silicates of chromium(II). Their bulk densities have been clearly decreased (to as low as below 250 g x L(-1) in the case of chromium(III) silicate), while capacities to absorb paraffin oil have increased to as much as 750 cm3 x 100 g(-1) for chromium(II) oxide. The respective particle size distribution has shown a tendency for disappearance of large accumulations of secondary agglomerates.
Aluminum-rich, hyperalkaline (pH > 13.5) and saline high-level nuclear waste (HLW) fluids at elevated temperatures (>50 degrees C), that possibly contained as much as 0.41 mol L(-1) Cr(VI), accidentally leaked to the sediments at the Hanford Site, WA. These extreme conditions promote base-induced dissolution of soil minerals which may affect Cr(VI)aq mobility. Our objective was to investigate Cr(VI)aq transport in sediments leached with HLW simulants at 50 degrees C, under CO2 and O2 free conditions. Results demonstrated that Cr(VI)aq fate was closely related to dissolution, and Cr(VI)aq mass loss was negligible in the first pore volumes but increased significantly thereafter. Similar to dissolution, Cr(VI)aq attenuation increased with increasing fluid residence time and NaOH concentration but decreased with Al concentrations in the leaching solutions. Aqueous Cr(VI) removal rate half-lives varied from 1.2 to 230 h with the fastest at the highest base concentration, lowest Al concentration, greatest reaction time, and lowest Cr(VI) concentration in the leaching solution. The rate of Cr(VI) removal (normalized to 1 kg of solution) varied from 0.83 x 10(-9) (+/-0.44 x 10(-9)) to 9.16 x 10(-9) (+/-1.10 x 10(-9)) mol s(-1). The predominant mechanism responsible for removing Cr(VI) from the aqueous phase appears to be homogeneous Cr(VI) reduction to Cr(III) by Fe(II) released during mineral dissolution. Cr(VI)aq removal was time-limited probably because it was controlled by the rate of Fe(II) release into the soil solution upon mineral dissolution, which was also a time-limited process, and other processes that may act to lower Fe(II)aq activity.