Reactivity of triesters of phosphoric acid in alkaline hydrolysis

Conclusions A difference in the alkaline hydrolysis rates of the triesters of phosphoric acid is determined by the sum of the induction effects of the alcohol radicals; the effect of the cleaved and remaining groups is equivalent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2595–2596.     

Polyesters of phosphoric acid: Synthesis and kinetics of hydrolysis

Three major methods have been elaborated in our laboratory for preparation of polymers with poly(alkylene phosphates) backbones: ring-opening polymerization, poly-condensation and transesterification, and polyaddition. The second method is based on the reaction of the commercially available compounds, namely dialkyl (or diaryl)-H-phosphonates and glycols. Reaction of the aliphatic H-phosphonates with aliphatic glycols is a reversible process, whereas polycondensation of diphenyl H-phosphonates with aliphatic and cycloaliphatic diols is practically irreversible. This latter method has recently been developed and is described in this paper. Poly H-phosphonates with M̄_n up to 40–10³ were prepared. Polymers are easily oxidized and quantitatively converted into the relatively stable poly(alkylene phosphates). Some physical properties of these polymers and kinetics of their hydrolysis is discussed.     

Coupled zinc transport through a bis(2-ethylhexyl)phosphoric acid solid-supported liquid membrane from aqueous perchlorate media

The rate of Zn(II) transport from 1.0 M (Na,H)ClO₄ aqueous media through a liquid membrane consisting of bis(2-ethylhexyl)phosphoric acid (HDEHP, HR) dissolved in Isopar-H and a teflon-type solid support, has been investigated as a function of the chemical composition of the system and the hydrodynamic conditions at 25°C. The measured transfer rates have been explained in terms of aqueous diffusion, diffusion of ZnR₂(HR)₂ and ZnR₂(HR) species through the liquid membrane and the rate of chemical reactions of Zn(II) in this system. The results are in agreement with the kinetic and equilibrium models proposed for this sytem in previous studies.     

Effect of sulfuric and phosphoric acid pretreatments on enzymatic hydrolysis of corn stover

The pretreatment of corn stover with H₂SO₄ and H₃PO₄ was investigated. Pretreatments were carried out from 30 to 120 min in a batch reactor at 121°C, with acid concentrations ranging from 0 to 2% (w/v) at a solid concentration of 5% (w/v). Pretreated corn stover was washed with distilled water until the filtrate was adjusted to pH 7.0, followed by surfactant swelling of the cellulosic fraction in a 0–10% (w/v) solution of Tween-80 at room temperature for 12 h. The dilute acid treatment proved to be a very effective method in terms of hemicellulose recovery and cellulose digetibility. Hemicellulose recovery was 62–90%, and enzymatic digestibility of the cellulose that remained in the solid was >80% with 2% (w/v) acid. In all cases studied, the performance of H₂SO₄ pretreatment (hemicellulose recovery and cellulose digestibility) was significantly better than obtained with H₃PO₄. Enzymatic hydrolysis was more effective using surfactant than without it, producing 10–20% more sugar. Furthermore, digestibility was investigated as a function of hemicellulose removal. It was found that digestibility was more directly related to hemicellulose removal than to delignification.     

Chemisorption of phosphoric acid and surface characterization of As passivated AlN powder against hydrolysis

By simply refluxing a commercial AlN powder in a mixture solution of ethanol, H(3)PO(4), and Al(H(2)PO(4))(3) for 24 h at 80 degrees C, the powder was successfully passivated against hydrolysis. The phosphate layer formed on the surface of AlN powder was found to be quite stable toward protecting the powder from hydrolysis. The efficacy of the coating was established by suspending the treated and the untreated powders in water for 72 h and subsequently characterizing them by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and Raman analysis. The good dispersing behavior of the treated AlN powder in water was confirmed by the low viscosity of an AlN suspension containing 50 vol % solids demonstrating the viability of replacing organic solvents by water in colloidal processing of AlN-based ceramics.     

The hydrolysis of phenylhydroxamic acid in concentrated aqueous sodium hydroxide

Phenylhydroxamic acid undergoes hydrolysis in concentrated NaOH via a complex mechanism: a maximum is observed in the plot of K_o versus [NaOH) which is attributed to the existence of one or more pre-equilibria influencing the rate-limiting step.     

Solubility of ammonia in aqueous solutions of phosphoric acid: Model development and application

A model to describe vapor-liquid equilibrium (VLE) and solid-liquid equilibrium (SLE) in the ammonia-phosphoric acid-water system is developed. The model takes into account chemical reactions as well as physical interactions. Using interaction parameters and solubility contants as determined from experimental data on VLE and SLE, the model is capable of describing the phase behavior in this extremely complex system over a wide range of composition.Dedicated to Prof. Dr.-Ing. G. Ernst on the occasion of his 60th birthday.     

Medium effects in the acid catalyzed hydrolysis of benzohydroxamic acid in binary aqueous mixtures

Hydrochloric acid catalyzed hydrolysis of benzohydroxamic acid (C₆H₅CONHOH) has been studied in dioxane, acetone, DMSO, DMF, methanol, ethanol and isopropanol of varying compositions (10–70 vol.%) at 55°C. The anomalous behavior has been explained on the basis of solvent properties, solvation of the transition state and dielectric constant.     

Inhibition of the oxygen evolution reaction during titanium passivation in aqueous phosphoric acid solution

Journal of Solid State Electrochemistry - The anodic oxide on titanium can be thickened by anodization, with the consequent corrosion properties of this oxide depending on many variables, including...     

Synthesis,characterization of SiO2 supported-industrial phosphoric acid catalyst for hydrolysis of NaBH4 solution

Abstract

Tunisian industrial phosphoric acid H₃PO₄ was supported on silica gel SiO₂ (SIPA) to catalyze the hydrolysis reaction of aqueous alkaline sodium borohydride (NaBH₄). The SiO₂ was produced from purified quartz sand using alkali fusion-acidification chemical process. The BET surface area results indicate that the prepared silica gel could reach a specific surface area up to 585 m²/g. The addition of PO₃H₂ functional groups resulted in an increase of surface acidity of SiO₂ catalyst as shown by FT-IR and DTA-DTG spectra. The total acidity of SIPA catalyst was determined by titration to be 2.8?mmol H⁺/g. SEM/EDS maps reveal the distribution of heavy metals on the silica surface. The effect of supported PO₃H₂ functional groups and heavy metals on the NaBH₄ hydrolysis reaction was studied for different ratios of SIPA catalyst to NaBH₄. The sample 12SIPA/NaBH₄ leads to a very high hydrogen generation rate (up to 90%). The activation energy of hydrogen generation by NaBH₄ hydrolysis was 25.7?kJ mol^?1.     

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     

Transpassive dissolution mechanism of ferrous alloys in phosphoric acid/acetic acid mixtures

The transpassive dissolution of Fe-12%Cr and Fe-25%Cr alloys in near-anhydrous phosphoric acid/acetic acid mixtures has been studied by conventional voltammetry and electrochemical impedance spectroscopy. Both steady-state and transient techniques point to two parallel pathways for the process involving oxidative dissolution of Cr as Cr(VI) and isovalent dissolution of Fe most probably mediated by an electrolyte-originating species. A simplified kinetic model of the process including only surface kinetic steps has been found to reproduce successfully both the steady-state and the small-amplitude AC response of the studied materials. The kinetic parameters of the model are determined and their relevance regarding the influence of the alloy and electrolyte composition on the relative importance of the two parallel pathways is discussed. The experimental data and model calculations indicate that the effect of acetic acid on the reaction steps related to dissolution of Fe is more significant.     

Natural radionuclide-free phosphoric acid production

High-uranium phosphate rock from Itataia, Brazil, was milled for wet-process phosphoric acid production using the dihydrate method. Uranium contained in the phosphoric acid was recovered by solvent extraction. The distribution of long-lived natural radionuclides of the ²³⁸U and ²³²Th decay series involved in these operations was evaluated. ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb were found to predominate in the phosphogypsum, while ²²⁸Th, ²³⁰Th and ²³²Th in the uranium-free phosphoric acid. Thorium is removed from the phosphoric acid by solvent extraction to produce a NORM-free phosphoric acid.     

Bentonite-based phosphoric acid organomineral cationite

The conditions under which bentonite-based phosphoric acid organomineral cationite is obtained were assessed and its acid-base and physicochemical properties were studied.     

Mechanism of 1,4,5,8-naphthalene tetracarboxylic acid dianhydride hydrolysis and formation in aqueous solution

The study of highly conjugated, carbonyl-containing molecules such as 1,4,5,8-naphthalene tetracarboxylic dianhydride, III, is of interest since reactivity differences and transmission of electronic effects through the conjugated framework can be evidenced. The kinetics of hydrolysis of III in aqueous solution were determined from 5 M acid to pH 10. In basic solution hydrolysis of III yields, sequentially, 1,4,5,8-naphthalene diacid monoanhydride, II, and 1,4,5,8-naphthalene tetracarboxylic acid, I. The second order rate constant for alkaline hydrolysis is 200 fold higher for the first ring opening. The water-catalyzed hydrolysis of III yields a pH-dependent mixture of ionic forms of I and II. The rate constant for water-catalyzed hydrolysis of III is 25 fold higher than that for II. In concentrated acid the rates for reaching equilibrium (I, II and III) increase and III is the major product. The pK(a)s of I (3.24, 5.13 and 6.25) and II (3.05, 5.90) were determined by potentiometric, fluorescence and UV spectroscopy titrations and by quantitative fit of the kinetic and equilibrium data. The apparent, pH-dependent, equilibrium constants, K(EqII), for anhydride formation between I and II were obtained from the UV spectra. The quantitative fit of kinetic and equilibrium data are consistent with the assumption that anhydride formation only proceeds with the fully protonated species for both I and II and permitted the estimation of the equilibrium constants for anhydride formation, K(EqII). The value of K(EqII) (I <==> II) between pH 1 and 6 was ca. 5. Geometry optimization calculations in the gas phase of the reactions of III in alkaline, neutral and acid conditions, at the DFT level of theory, gave electronic distributions that were qualitatively consistent with the experimental results.     

On-line FT-Raman spectroscopic monitoring of starch gelatinisation and enzyme catalysed starch hydrolysis

The hydrolysis of starch by α-amylase and amyloglucosidase and the kinetics of these technically important reactions were investigated by FT-Raman spectroscopy. During the technical starch hydrolysis process, three reactions proceed one after the other but partly in parallel: the gelatinisation, the hydrolysis of starch to dextrin (liquefaction) by α-amylase, and the hydrolysis of dextrin to glucose (saccharification) by glucoamylase. These three reactions were studied separately. Potato starch or dextrin in concentrations of 50 g/l were suspended or dissolved in water, the reaction chamber was placed in a heated water bath, and defined, varied amounts of enzymes in solution were added. The reactions were monitored on-line in a bypass loop. The greatest spectral changes were observed due to the swelling and gelatinisation of starch. The liquefaction of starch to dextrin was started with the addition of α-amylase at a temperature of 80°C and the spectral changes were monitored. In a similar way, a solution/suspension of dextrin was used to investigate the reaction of glucoamylase at 50°C. Both enzymatic reactions were performed at four different enzyme activities. All reactions showed distinctive spectral changes, which can, in principle, be evaluated for the determination of the degree of starch hydrolysis. As a Nd:YAG laser at 1064 nm was used, fluorescence excitation was not observed despite the use of crude, technical-grade enzymes. The findings demonstrate the potential use of Raman spectroscopy in monitoring and control of technical enzyme reactions.     

Extraction of neodymium and europium by bis-(2-ethylhexyl) phosphoric acid from aqueous diamine solutions

The extraction of Nd³⁺ and Eu³⁺ from aqueous media containing selected diamine ligands by HDEHP solution in benzene has been investigated. It is found that the presence of the diamine in the aqueous phase enhances the extraction of both Nd³⁺ and Eu³ in the organic phase. The possible explanation for this behaviour is presented and a mechanism based on extraction of an adduct of the type MH₃(DEHP)₆. B is found to be the most probable.