The analytical kinetics of the titanium(III)-perchlorate reaction-I Homogeneous reaction kinetics

A spectrophotometric investigation has been made of the analytically relevant kinetics of the titanium(III)-perchlorate reaction in chloride and sulphate media. Sulphate media give better and more reproducible results. The reaction in sulphate medium is first-order in titanium(III) and hydrogen ion, but of fractional order in perchlorate. The pseudo third-order rate constant k(3)' for the rate equation has a value of 4.22 +/- 0.15 l(2) mol(-2) s(-1) at 49 degrees C. The energy of activation in sulphate medium is 84 +/- 4 kJ mol(-1), and in chloride medium is 80 +/- 12 kJ mol(-1). Small amounts of chloride m a sulphate medium, or of sulphate in a chloride medium, retard the reaction. The basis has been laid for a rate-measurement method for determination of perchlorate at low concentrations.     

Equilibrium and kinetics study of uranium(VI) from aqueous solution by Citrus limetta peels

The potential of the biowaste Citrus limetta peels (CLP) was assessed for adsorption of uranium(VI) from uranyl nitrate solution. Maximum adsorption capacity of 75.33 mg g^?1 was achieved at pH 4, showing drastic falls thereafter. This was attributed to the presence of UO₂ ²⁺, UO₂OH⁺, (UO₂)₃(OH)⁵⁺ and (UO₂)₂(OH) ₂ ²⁺ ions. The peels were characterized for elucidating the role of functional groups and morphology on the sorption capacity. The isotherm studies revealed that Langmuir, Freundlich as well as Sips models give the best fit for the experimental data observing pseudo second order kinetics. The equilibrium was achieved in 90 min. The adsorption shows complex mechanism, took place by both physical and ion-exchange mechanism.     

The kinetics and mechanism of reaction between ethylenediaminetetraacetomanganate(III) and cyanide ion

Summary The title reaction has been followed spectrophotometrically at 325 nm (_max of [Mn(CN)₆]^3–) under pseudo-first order conditions with cyanide in a large excess at pH=10.0, I=0.1M (NaClO₄) and 25°C. The reaction follows first-order kinetics in [MnEDTA(OH)]^2– and exhibits variable-order dependence in [CN^–] one at high cyanide concentration, and two at low cyanide concentration. The product of above reaction has been identified as [Mn(CN)₆]^3–.The kinetics of the reverse reaction,i.e., the reaction of [Mn(CN)₆]^3- with EDTA^4– have also been followed spectrophotometrically. This reactions is first-order with respect to both [Mn(CN) ₆ ^3– ] and [EDTA^4–] and exhibits an inverse first-order dependence on [CN^–]. A six-step mechanism has been proposed in which the penultimate step is rate-determining. The activation parameters have been obtained and support the postulated mechanism.     

The kinetics of the anation reaction of aquopentaamminecobalt(III) by malonate in acidic aqueous solution

The Co(NH₃)₅OH₂³⁺ ion reacts with malonate to form Co(NH₃)₅O₂CCH₂CO₂H²⁺ or Co(NH₃)₅O₂CCH₂CO₂⁺, depending on the pH of the reaction solution. The kinetics of this anation reaction have been studied as a function of [H⁺] for the acidity range 1.5 ≤ pH ≤ 6.0 in the temperature range of 60 to 80°C, the [total malonate] ≤ 0.5 M, and the ionic strength 1.0M. The anation by malonic acid follows second-order kinetics, the rate constant being 8.0 × 10^?5 M^?1·sec^?1 at 70°C, and the anations by bimalonate (Q₁, k₁) and malonate ion (Q₂, k₂) are consistent with an I_d mechanism. Typical values at 70°C for the ion pair formation constants are Q₁ = 1.3, Q₂ = 5.4M^?1; and for the interchange rate constants k₁ = 5.3 × 10^?4; k₂ = 7.3 × 10^?4 sec^?1. The activation parameters for the various rate constants are reported and the results discussed with reference to previously reported data for similar systems.     

The reaction between oxalatotetraammine-cobalt(III) ion and hydroxide ion in aqueous solution

The rate of the reaction between sodium hydroxide and oxalatotetraamminecobalt(III) ion was measured for a variety of hydroxide ion concentrations and at four temperatures. The rate law below 333 K is given by k_obs = k₀ + k₂[OH⁻]² and above 333 K is shown to be k_obs = k₀ + k₁[OH⁻]. The reaction proceeds with a single rate controlling step, which is interpreted as oxalate ring opening. This is followed by a rapid oxalate loss step.     

Interaction mechanisms between uranium(VI) and rutile titanium dioxide: from single crystal to powder

This paper is devoted to the study of the mechanisms of interaction between uranyl ion and rutile TiO2. Among the radionuclides of interest, U(VI) can be considered as a model of the radionuclides oxo-cations. The substrate under study here is the rutile titanium dioxide (TiO2) which is an interesting candidate as a methodological solid since it can be easily found as powder and as manufactured single crystals. This material presents also a wide domain of stability as a function of pH. Then, it allows the study of the retention processes on well-defined crystallographic planes, which can lead to a better understanding of the surface reaction mechanisms. Moreover, it is well-established that the (110) crystallographic orientation is dominating the surface chemistry of the rutile powder. Therefore, the spectroscopic results obtained for the U(VI)/rutile (110) system and other relevant crystallographic orientations were used to have some insight on the nature of the uranium surface complexes formed on rutile powder. This goal was achieved by using time-resolved laser-induced fluorescence spectroscopy (TRLFS) which allows the investigation, at a molecular scale, of the nature of the reactive surface sites as well as the surface species. For rutile surfaces, oxygen atoms can be 3-fold, 2-fold (bridging oxygens), or single-fold (top oxygens) coordinated to titanium atoms. However, among these three types of surface oxygen atoms, the 3-fold coordinated ones are not reactive toward water molecules or aqueous metallic cations. This study led to conclude on the presence of two uranium(VI) surface complexes: the first one corresponds to the sorption of aquo UO22+ ion sorbed on two bridging oxygen atoms, while the second one, which is favored at higher surface coverages, corresponds to the retention of UO22+ by one bridging and one top oxygen atom. Thus, the approach presented in this paper allows the establishment of experimental constraints that have to be taken into account in the modeling of the sorption mechanisms.     

Adsorption of uranium (VI) from aqueous solution by tetraphenylimidodiphosphinate

The adsorption of uranium (VI) using tetraphenylimidodiphosphinate (Htpip) was studied. Factors of affecting sorption efficiency have been investigated and results showed the adsorption of uranium (VI) was equilibrium at pH 4.5, time 20 min, adsorbent dosage 0.005 g and initial concentration 50 mg L^?1 reaching 99.86 mg g^?1 of adsorption capacity and 99.86% of removal efficiency. Additionally, the interfering ions studies showed that the adsorbent possessed excellent adsorption selectivity of uranium (VI). The surface morphology of Htpip was investigated by SEM. The adsorption process of uranium (VI) onto Htpip fit the pseudo-second-order kinetic model and the Freundlich isotherm model very well.     

Thermal behaviour of co-precipitated mixtures of chromium(III) and uranium(VI)

In the CrUO system, besides the phases reported earlier, a triuranate CrU₃O_10-x (x ～ 0.3) could be identified. It is unstable above 70o°C and decomposes to a mixture of CrUO₄ and U₃O₈. Under reducing atmospheres up to 1600°C, the uranium—chromium—oxygen system gives a mixture of Cr₂O₃ and UO₂. No new phase could be identified. The compound CrUO₄ is unstable under reducing conditions and decomposes to a mixture of Cr₂O₃ and UO₂.     

Role of anions and reaction conditions in the preparation of uranium(VI), neptunium(VI), and plutonium(VI) borates

U(VI), Np(VI), and Pu(VI) borates with the formula AnO(2)[B(8)O(11)(OH)(4)] (An = U, Np, Pu) have been prepared via the reactions of U(VI) nitrate, Np(VI) perchlorate, or Pu(IV) or Pu(VI) nitrate with molten boric acid. These compounds are all isotypic and consist of a linear actinyl(VI) cation, AnO(2)(2+), surrounded by BO(3) triangles and BO(4) tetrahedra to create an AnO(8) hexagonal bipyramidal environment. The actinyl bond lengths are consistent with actinide contraction across this series. The borate anions bridge between actinyl units to create sheets. Additional BO(3) triangles and BO(4) tetrahedra extend from the polyborate layers and connect these sheets together to form a three-dimensional chiral framework structure. UV-vis-NIR absorption and fluorescence spectroscopy confirms the hexavalent oxidation state in all three compounds. Bond-valence parameters are developed for Np(VI).     

Electrochemical kinetics of the hydrogen reaction on platinum in concentrated HCl(aq)

The hydrogen reaction in concentrated HCl(aq) solutions is a key reaction for the CuCl(aq)/HCl(aq) electrolytic cell. Here, electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) were used to obtain new data for the hydrogen reaction on platinum submerged in highly concentrated acidic solutions at 25 °C and 0.1 MPa. LSV and EIS data were collected for Pt in 0.5 mol/L H₂SO₄(aq), 1 mol/L HCl(aq) and 7.71 mol/L HCl(aq) solutions. It was found that exchange current density (j₀) values varied between 1 and 2 mA/cm². An equivalent circuit model was used to obtain comparable j₀ and limiting current density values from EIS data relative to values obtained with LSV data. It was found that as the concentration of acid increased, a noticeable decrease in the performance was observed.     

Kinetics and mechanism of solid-state reaction between bismuth(III) oxide and molybdenum(VI) oxide

The mechanism of the following solid-state reactions between bismuth(III) oxide and molybdenum(VI) oxide was investigated within the temperature range 400–650°C.

$\text{(i)}\text{Bi}{}_2\text{O}{}_3\text{+ MoO}{}_3\text{→ Bi}{}_2\text{MoO}{}_6\text{, (ii)}\text{Bi}{}_2\text{O}{}_3\text{+ 2MoO}{}_3\text{→ Bi}{}_2\text{MO}{}_2\text{O}{}_9\text{, (iii)}\text{Bi}{}_2\text{O}{}_3\text{+ 3MoO}{}_3\text{→ Bi}{}_2\text{(MOO}{}_4\text{)}{}_3\text{, (iv)}\text{Bi}{}_2\text{MoO}{}_6\text{+ MoO}{}_3\text{→ Bi}{}_2\text{MO}{}_2\text{O}{}_9\text{, (v)}\text{Bi}{}_2\text{Mo}{}_2\text{O}{}_9\text{+ MoO}{}_3\text{→ Bi}{}_2\text{(MoO}{}_{\mathrm{2)3}}\text{.}$

Two types of experiments, capillary and particle size, were performed to ascertain whether MoO₃ diffuses into Bi₂O₃ or vice versa. These show that molybdenum trioxide diffuses into bismuth oxide grains. If α is the fraction of molybdenum trioxide reacted, the kinetics in all five cases are found to be governed by the equation αⁿ = kt throughout the temperature range, where n and k are constants at a given temperature and t is the time. Both n and k are temperature dependent. The characteristic feature of these reactions is that they proceed to completion. Results are also fitted by the relation $\text{α = k}{}_2\text{t}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{? k}{}_3\text{t}$, where k₂ and k₃ are constants, which shows that the reactions occur by bulk diffusion through grain boundary contacts. The number of grain boundary contact points decreases with time in the course of reaction.     

Biosorption of uranium(VI) from aqueous solution by Citrus limon peels: kinetics,equlibrium and batch studies

Citrus limon peel (exocarp) was chemically treated and used for removal of U(VI) ions from aqueous solution in a batch system. Optimization of U(VI) sorption parameters, i.e. medium pH, adsorbent amount, contact time, initial U(VI) ions concentration and temperature on the removal performance of both native and modified peels was studied. Adsorption capacity of the modified peel was near up to 4 times higher than of unmodified. The correlation regression coefficients show that the adsorption process can be well-defined by Langmuir equation. Additionally, it conforms to the pseudo-second order kinetic and Weber–Morris diffussion models well.

     

Extraction of uranium (VI) from sulfuric acid solution with TOPO

The extraction of uranium(VI) from sulfuric acid medium with tri-octylphosphine oxide (TOPO) in n-heptane was studied. Accompanied with the increase in the concentration of H₂SO₄, the distribution coefficient of uranium(VI) increased in the region of dilute sulfuric acid. When the concentration of H₂SO₄ surpassed 3.5 mol·dm⁻³, the distribution coefficient of uranium(VI) was at maximum. This result was due to the competition extraction between uranium(VI) and H₂SO₄. From the data, the composition of extracted species and the equilibrium constant of extraction reaction have been evaluated, which were (TOPOH)₂UO₂(SO₄)₂ (TOPO) and 10^7.6±0.15, respectively.     

Removal of uranium(VI) from aqueous solution using sponge iron

Direct reduced iron (DRI), also called sponge iron, was used for the removal of U(VI) from aqueous solution. Batch experiments were conducted to evaluate the effect of various factors including contact time, solution pH, DRI dosage and initial uranium concentration on this removal process. The result suggested that U(VI) can be rapidly removed by DRI and this removal process followed an apparent first-order reaction kinetics. The optimum pH for uranium removal was between 2.0 and 4.0. Whether U(VI) can be fully removed was influenced by the molar ratio of DRI to U(VI) in solution. The aqueous U(VI) can be removed completely when this ratio was more than ca. 1,000. The U(VI) removal capacities of DRI decreased with increasing DRI dosages at a constant concentration of U(VI), but increased almost linearly with increasing initial U(VI) concentrations at a fixed dosage of DRI. The maximum U(VI) removal capacity was 5.71 mg/g DRI. Finally, the possible mechanism of U(VI) removal by DRI was also discussed. The XPS and XRD analysis showed that U(VI) was deposited as UO₃ onto DRI surface, indicating that U(VI) can be removed without reduction.