On the acidity of liquid and solid acid catalysts. Part 3. Esterification of benzoic and mesitoic acids

Methyl esters of benzoic and mesitoic acid have been prepared with high yields (>98 wt%) from the corresponding carboxylic acids + methanol in aprotic solvents over samples of H₂SO₄/SiO₂ at 60°C. The results show a high catalytic efficiency of the solids but also suggest an acid strength comparable to that observed in concentrated aqueous H₂SO₄ (range >90 wt%) when the acid requirements for the esterification of analogous compounds in aqueous acid solutions are taken into account. Indeed, different reacting species, i.e., ArC(OH) ₂ ⁺ from benzoic acid and 2,4,6‐triMe‐ArC=O⁺ from mesitoic acid are involved in the esterification, but the mesitoyl cation can be formed and esterified in the acidity ranges between 92 and 98 wt% H₂SO₄. This revised version was published online in July 2006 with corrections to the Cover Date.     

A quantum‐chemical study of the formation mechanism and nature of tert‐butyl carbenium ions in 100% sulfuric acid

Ab initio quantum‐chemical calculations reveal that the interaction of isobutene with H₃SO ₄ ⁺ ions produced by self‐dissociation of sulfuric acid occurs virtually without an activation barrier, whereas the reactions involving neutral species of sulfuric acid are characterized by considerable activation barriers: 14.9 kcal/mol at the MP2(full)/6‐31+G*//6-31+G* level and 16.9 kcal/mol^-1 at the MP2(full)/6‐31+G*//3‐21+G* level. It is also concluded that the species resulting from interaction of isobutane with H₃SO ₄ ⁺ ions of protonated tert‐butyl sulfuric acid are ion‐molecular complexes which should be considered as tert‐butyl carbenium ions weakly solvated by H₂SO₄ molecules. Although the concentration of these species in concentrated sulfuric acid is very low, presumably, they play a role of active intermediates in isobutene conversions catalyzed by sulfuric acid. This revised version was published online in July 2006 with corrections to the Cover Date.     

On the acidity of liquid and solid acid catalysts: Part 1. A thermodynamic point of view

The protonation equilibria of weak bases (B) in solid acids (HClO₄/SiO₂, CF₃SO₃H/SiO₂, H₂SO₄/SiO₂) were studied by UV spectroscopy and the results were compared to those obtained for analogous compounds in concentrated aqueous solutions of strong acids (HClO₄, CF₃SO₃H, H₂SO₄). The behaviour of B in liquid (L) and solid (S) phase was analysed by titration curves, log[BH⁺]/[B] ratios and thermodynamic pK _BH+ values. It has been shown that the proton transfer process acid → base (i.e., from (H+A^-)_(L,S) to (BH+A^-)_(L,S)} can be described by the relationship observed between the activity coefficient terms that are to be taken into account for acid–base equilibria occurring in nonideal systems ( – log(f _B f _B+/f _BH+)_(L,S)= -n _BA log(f _A–f _H+/f _HA)_(L,S)) and can be estimated by the n _BA values. Two “activity coefficient functions” (i.e., Mc(B) = – log(f _B f _B+/f _BH+)and Mc(s) = – log(f _A–f _H+/f _HA)) were used to describe, respectively, the equilibria of B and the equilibria of the acids in concentrated aqueous solutions and the meaning of terms “activity coefficient function” and “protonating ability of an acid” were discussed. The difference between “acidity functions”, determined for solutes (Ac(i)) and solvents (Ac(s)) in aqueous acids, and the H_x acidity functions, the latter developed for solutes in analogous media by the Hammett procedure, was also shown. This revised version was published online in July 2006 with corrections to the Cover Date.     

Determination of the kinetics of chlorobenzene nitration using a homogeneously continuous microflow

The nitration of chlorobenzene with concentrated mixed acids is a fast and highly exothermic process, which suffers from considerable mass transfer resistance and poor heat transfer rates. The reaction kinetics has not been thoroughly reported before. In this work, a continuous-flow microreactor system and a homogeneous reaction condition were proposed to obtain accurate chlorobenzene nitration kinetics parameters at high mixed acid concentrations. A general model for predicting the observed reaction rate constants was established. With a new method for estimating the equilibria associated with HNO₃ in aqueous sulfuric acid, the rate constants based on nitronium ion and activation energies were obtained. Compared with batch reactors, the continuous-flow microreactor system allows for a sufficient heat transfer efficiency and accurate residence time control, making it possible to study the reaction performance more quickly and sensitively. This work may provide a reliable reference for the kinetic study of similar processes.     

Aqueous speciation of arsenic in sulfuric acid and cupric sulfate solutions

Physicochemical data for arsenic speciation calculations, and the development and application of an equilibrium model were determined numerically and experimentally to simulate the speciation of arsenic and copper in aqueous sulfuric acid solutions. Results show that concentrations of dissolved species depended highly on temperature, acidity, and solution concentration. A range of species can be formed, depending on pH and temperature. In acidic solutions, the principal ones are: HSO₄⁻, H⁺, Cu²⁺, CuSO_4(aq), H₃AsO_3(aq), and H₃AsO_4(aq); arsenic ions are present in low concentrations. Association degrees increase with temperature and concentration, the solutes being partially dissociated. Calculations of metal solubilities, pH, and ionic conductivity showed good agreement with experimental data. The model can be applied to study the aqueous speciation in industrial copper hydrometallurgical solutions, as well as to define and to evaluate purification strategies for the treatment of industrial effluents.     

Investigation of optimal conditions for zinc electrowinning from aqueous sulfuric acid electrolytes

Results are reported of an experimental investigation of the effects of aqueous zinc(II) and sulfuric acid concentrations on current efficiencies and deposit morphologies of metallic zinc, aimed at designing a process for zinc recovery from solid industrial wastes by leaching and electrodeposition. Voltammetry and chronopotentiometry of additive-free solutions of zinc(II) sulfate and sulfuric acid were used to determine the zinc(II) reduction kinetics, prior to investigating the deposition in a Hull cell to observe the effects of the current density and the bath composition on current efficiencies and deposit morphologies. For a current density of 45 mA cm⁻², best performance was obtained with zinc(II) concentrations of the same order of magnitude as the H⁺ concentration; too acidic solutions resulted in lower current yields and pronounced 3-D growth of the deposit.     

NMR study of the role of isopropylsulfates in the two-step “conjunct oligomerization” of propylene and isopentane–propylene alkylation catalyzed by 95% sulfuric acid

“Conjunct oligomerization” of propylene or the isopentane–propylene alkylation catalyzed by an excess of 95% sulfuric acid was performed in two consecutive steps. First di-isopropylsulfate was prepared by interaction of sulfuric acid with propylene. The ester was then either decomposed at room temperature in the presence of the 5–10 molar excess of 95% acid or was used in the acid-catalyzed alkylation of isopentane. In situ ¹H and ¹³C NMR study of the reaction mixture of “conjunct oligomerization” indicated that the diester participates in two equilibria with sulfuric acid. The first one transforms the diester into a monoester. The second equilibrium corresponds to protonation of the monoester with an excess of sulfuric acid. This converts a minor fraction of the mono-alkylsulfate into isopropyl carbenium ions that are only weakly solvated with sulfuric acid: C₃H₇HSO₄ + H₂SO₄ ⇄ C₃H₇ ⁺ H₂SO₄ + HSO₄ ⁻. The subsequent reactions of alkyl carbenium ions with the non-protonated alkylsulfate result in final products of “conjunct oligomerization” while in the presence in the reaction mixture of isopentane, alkylation with the predominant formation of C₈ branched paraffins takes place. A very low yield of propane indicates a minor role of hydride transfer in alkylation. Another unexpected result is the absence in both reaction mixtures of propylene. These findings are in contradiction with the classical mechanism of isoparaffin–olefin alkylation by Schmerling. Therefore, an alternative mechanism of this reaction is suggested via a direct alkylation of isopentane with the mono-alkylsulfate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Aspects of the surface and bulk nitration of cellulose in nitric acid,nitric acid/water,and nitric acid/dichloromethane mixes

Electron spectroscopy for chemical analysis (ESCA) has been employed to follow the surface nitration of cellulose papers in nitric acid–water and nitric acid–dichloromethane mixes with the aim of: elucidating the identity of the nitrating species in these mixes and from comparison of surface and bulk degree of substitution (DOS) further understanding on the role that morphology plays in the nitration of cellulose in these mixes. In nitric acid, nitric acid–water and nitric acid–dichloromethane mixes, surface nitration was observed to be slow (cf. to that reported in mixed acids) and the concentration of nitronium ion was observed to be low (cf. to mixed acids). On the basis of these observations and from the results of kinetic experiments, reported herein, it is proposed that the nitronium ion, NO₂⁺, is the important nitrating species of cellulose in these nitric acid mixes. Nitration in all but the most concentrated nitric acid–dichloromethane mixes produced equal surface and bulk DOS; however, nitration in pure nitric acid produced different surface and bulk DOS. The latter result implies that the heterogeneous nature of the nitration reaction can influence the DOS achieved.     

Study of ClO2 generation reaction via experimental data of aqueous mixed electrolyte solutions: HClO4–NaCLO3–H2O and HCLO4–NaCl–H2O

A new model for mixtures (two and more solutes) of aqueous electrolyte solutions was found to be as accurate as other models, or more accurate, in prediction of new experimental results of the ternary systems HClO₄–NaClO₃–H₂O and HClO₄–NaCl–H₂O. The water activity values are then used to study the mechanism of the chloride–chlorate reaction, generating chlorine dioxide: 2H⁺ + ClO^?₃ + Cl^? → ClO₂ + 1/2Cl₂ + H₂O Spectrophotometric measurements of the production rate of ClO₂ have confirmed that the intermediary species in the proposed equilibrium H⁺(mH₂O) → H⁺(m-n)H₂O + nH₂O Is actually H(H₂0)⁺_m-n. The final kinetic expression for the reaction rate of chlorine dioxide generation, used in pulp bleaching, is then derived to explain the high order with respect to acid concentration.     

A Spectrophotometric Study of Trivalent Actinide Complexes in Solution. IV. Americium with Chloride Ligands

The light absorption spectra of americium(III) in ethanolic and concentrated aqueous lithium chloride solutions, and in long-chain alkylammonium chloride solutions in aromatic diluents were obtained, as well as those of certain solid double salts and complexes. A strong 5f⁶ → 5f⁵6d¹ transition was observed in the aqueous solutions at 235 nm (42,500 cm^?1), and from the dependence of the intensity of this and the 503 nm (19,880 cm^?1) band, on the effective chloride activity, the stability constants of the inner sphere complexes: AmCl²⁺, logβ₁^* = ?2.21± 0.08, and AmCl₂⁺, log β₂^* = ?4.70 ± 0.08, were determined. The spectrum of the long-chain amine extracts is comparable to that of solids of the composition AmCl₃ · 2N(C₄H₉)₄Cl · × LiCl, and the nature of the extracts and of this and similar solids is discussed.     

Diffraction Studies on Concentrated Aqueous Hydrochloric Acid Solutions

X-ray diffraction and neutron diffraction experiments with H/D isotopically substituted aqueous 21 mol% hydrochloric acid solutions were carried out in order to obtain detailed features concerning the intermolecular hydrogen-bonded structure in highly concentrated aqueous acidic solutions. Structure parameters, namely, intermolecular distance, root-mean-square amplitude, and coordination number, for the nearest neighbor H₃O⁺···H₂O interaction were determined from the least-squares-fitting analysis of the observed X-ray interference term. These were, respectively, r(H₃O⁺···H₂O) = 2.45(1) Å; l(H₃O⁺···H₂O) = 0.11(1) Å; and n(H₃O⁺···H₂O) = 1.8(1). The intermolecular nearest neighbor distances, r(H···H) = 2.02(5) Å and r(O···H) = 1.69(2) Å, were determined from the least-squares fit to partial structure factors, a_ij (Q), derived from the observed neutron intermolecular interference terms for sample solutions with different H/D isotopic ratios. The present values of intermolecular distances are significantly shorter than those for pure liquid water, implying that extremely strong hydrogen bonds exist in concentrated aqueous acidic solutions.     

Raman and kinetic evidence of NO2+ ion in solid acid catalysts

Samples of H₂SO₄/SiO₂ loaded with HNO₃ and analysed by Raman spectroscopy exhibit the band of the NO₂⁺ ion, which is formed by the protonation–dehydration equilibrium of HNO₃ in strong acidic media. The effectiveness of NO₂⁺ as a nitrating species is tested in the nitration of aromatic compounds towards substrates with high acid requirements for the conversion reagents–products. The acidic properties of the acid systems used as catalysts are also described, and the thermodynamic parameters related to the acid–base proton transfer process are discussed.     

The electrochemical hydrogenation of edible oils in a solid polymer electrolyte reactor. I. Reactor design and operation

A new electrochemical method has been devised and tested for the moderate temperature/atmospheric pressure hydrogenation of edible oils, fatty acids, and fatty acid methyl esters. The method employed a solid polymer electrolyte (SPE) reactor, similar to that used in H₂/O₂ fuel cells, with water as the source of hydrogen. The key component of the reactor was a membrane-electrode-assembly, composed of a RuO₂ powder anode and either a Pt-black or Pd-black powder cathode that were hot-pressed as thin films onto the opposing surfaces of a Nafion cation-exchange membrane. During reactor operation at a constant applied current, water was back-fed to the RuO₂ anode, where it was oxidized electrochemically to O₂ and H⁺. Protons migrated through the Nafion membrane under the influence of the applied electric field and contacted the Pt or Pd cathode, where they were reduced to atomic and molecular hydrogen. Oil was circulated past the back side of the cathode and unsaturated triglycerides reacted with the electrogenerated hydrogen species. The SPE reactor was operated successfully at a constant applied current density of 0.10 A/cm² and a temperature between 50 and 80°C with soybean, canola, and cottonseed oils and with mixtures of fatty acids and fatty acid methyl esters. Reaction products with iodine values in the range of 60–105 were characterized by a higher stearic acid content and a lower percentage of trans isomers than those produced in a traditional hydrogenation process.     

Electrochemical preparation of peroxodisulfuric acid using boron doped diamond thin film electrodes

We have investigated the electrochemical oxidation of sulfuric acid on boron-doped synthetic diamond electrodes (BDD) obtained by HF CVD on p-Si. The results have shown that high current efficiency for sulfuric acid oxidation to peroxodisulfuric acid can be achieved in concentrated H₂SO₄ (>2 M) at moderate temperatures (8-10 °C). The main side reaction is oxygen evolution. Small amounts of peroxomonosulfuric acid (Caro's acid) have also been detected. A reaction mechanism involving hydroxyl radicals, HSO₄⁻ and undissociated H₂SO₄ has been proposed. According to this mechanism electrogenerated hydroxyl radicals at the BDD anode react with HSO₄⁻ and H₂SO₄ giving peroxodisulfate.     

Modeling of aqueous electrolyte solutions based on perturbed-chain statistical associating fluid theory incorporated with primitive mean spherical approximation

In this work an equation of state applicable to the system containing electrolytes has been developed by coupling the perturbed chain statistical associating fluid theory (PC-SAFT) with the primitive mean spherical approximation. The resulting electrolyte equation of state is characterized by 4 ion parameters for each of the cation and anion contained in aqueous solutions, and 4 ion specific parameters for each of six cations (Li⁺, Na⁺, K⁺, Rb⁺, Mg²⁺ and Ca²⁺) and six anions (Cl⁻, Br⁻, I⁻, HCO₃⁻, NO₃⁻ and SO₄²⁻) were estimated, based upon the individual ion approach, from the fitting of experimental densities and mean ionic activity coefficients of 26 aqueous single-salt solutions at 298.15 K and 1 bar. The present equation of state with the estimated individual ion parameters has been found to satisfactorily describe not only the densities and mean ionic activity coefficients, but also osmotic coefficients and water activities of single-salt aqueous solutions. Furthermore, the present model was extended to two-salt aqueous solutions, and it has been found that thermodynamic properties such as mentioned above, of two-salt solutions, can be well predicted with the present model, without any additional adjustable parameters.     

A study on acid reclamation and copper recovery using low pressure nanofiltration membrane

In this study, nanofiltration membrane is used to separate proton (H⁺) and copper ions from a ternary ions mixture (H⁺, Cu²⁺, SO₄^2?). The performance of membrane in separating Cu²⁺ and H⁺ was tested under the effect of pressure, concentration and different acid strength (pH). It was found that the H⁺ rejection is independent of the applied pressure. Permeability of solution decreased linearly with the increase of CuSO₄ concentration. In terms of H⁺ rejection, there is a continuous drop in rejection from 0.1 mM CuSO₄ to 10 mM CuSO₄ solution. H⁺ was poorly retained and concentrated in the permeate stream in corresponding to the electro-neutrality requirements, on the other hand, the rejection of copper ion was almost constant with pH. In overall, optimum acid reclamation and copper recovery can be achieved at higher volume flux. A Three Parameters-Combined Film-Extended Nernst-Planck Equation (CF-ENP) model is successfully applied to predict the performance of nanofiltration membrane in separating the ternary ions.     

Wet oxidation of acetic acid by H2O2 catalyzed by transition metal-exchanged NaY zeolites

During the wet oxidation of contaminated wastewaters, the destruction of low molecular weight carboxylic acid intermediates such as acetic, glyoxalic, and oxalic acids is often the rate-controlling step. Oxidation of acetic acid, a very recalcitrant intermediate, requires compelling treatment severity. Heterogeneous catalytic wet oxidation of model acetic acid aqueous solutions was conducted under mild conditions (below the normal boiling point of water) using hydrogen peroxide over various transition metal-exchanged NaY zeolites. Treatment of Cu²⁺–NaY with oxalic acid [OA] led to a catalyst, Cu²⁺–NaY [OA], with significantly improved properties in terms of total organic carbon (TOC) removal efficiency and catalyst stability against leaching. This catalyst outperformed homogeneous Cu²⁺ by a factor of 2–2·5 times. Continuous feeding of H₂O₂ reduced its undesirable decomposition. Improvement of the TOC-degradation performance by Cu²⁺–NaY [OA] was tentatively attributed to the removal of sodium and possibly aluminium in the zeolite. © 1998 Society of Chemical Industry     

Grafting onto wool. XXVIII. Effects of acids on gamma-radiation induced graft copolymerization of ethylmethacrylate onto wool fiber

Graft copolymerization of ethylmethacrylate (EMA) onto Himachali wool fiber has been investigated in aqueous medium by mutual gamma irradiation from a Co⁶⁰ source in air and in nitrogen atmosphere. Percentage of grafting has been evaluated as a function of (i) total dose, (ii) concentration of monomer, and (iii) effect of concentration of different acids such as hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, and acetic acid. Maximum percentage of grafting has been obtained in the presence of sulfuric acid. Following reactivity order of different acids towards grafting has been observed: H₂SO₄ > HCI > HNO₃ > HCIO₄ > CH₃COOH. A plausible mechanism to explain the effect of acids on percentage of grafting of EMA has been suggested.     

Simulation of SO2 absorption into sulfuric acid solutions containing hydrogen peroxide in the fast and moderately fast kinetic regimes

Absorption of sulfur dioxide into aqueous solutions containing hydrogen peroxide results in the irreversible oxidation to sulfuric acid. As shown in previous works, the absorption rate increases with the concentration of oxidizing agent but decreases with the rise of acidity. This paper presents a thorough kinetic investigation of the liquid-phase reaction of SO₂ for a wide range of H₂O₂ and H₂SO₄ concentrations.Absorption of sulfur dioxide was carried out at 20 °C in a pilot-scale packed column. The experimental data were modelled thanks to the theory of absorption in the fast or moderately fast chemical reaction regimes defined by classical Hatta numbers and depending on the H₂O₂ concentration at a given acidity. For both regimes, a satisfactory agreement was obtained between experimental results and predictions of models including original values of kinetic parameters.     

Equilibrium Analysis of Aggregation Behavior in the Solvent Extraction of Cu(II) from Sulfuric Acid by Didodecylnaphthalene Sulfonic Acid

Abstract

By use of the principles of equilibrium analysis, the liquid-liquid cation exchange of Cu(II) from aqueous sulfuric acid at 25°C by didodecylnaphthalenesulfonic acid (HDDNS) in toluene may be understood in terms of small hydrated aggregated species in the organic phase. Extraction data have been measured as a function of organic-phase HDDNS molarity (1.0 × 10^?4 to 1.0 × 10^?1), aqueous copper(II) sulfate molarity (1.2 × 10^?8 to 1.3 × 10^?2), and aqueous sulfuric acid molarity (0.03 to 6.0). Graphical analysis of linear regions of the data support a model in which organic-phase aggregates of HDDNS function by cation exchange to incorporate Cu(II) ions with no apparent change in aggregation number at low loading. Supporting FTIR spectra and water-content measurements of HDDNS solutions in toluene show that the HDDNS aggregates are highly hydrated. By use of the computer program SXLSQA, a comprehensive equilibrium model was developed with inclusion of activity effects. Aqueous-phase activity coefficients and degree of aqueous bisulfate formation were estimated by use of the Pitzer treatment. Organic-phase nonideality was estimated by the Hildebrand-Scott treatment and was shown to be a negligible effect under the conditions tested. Excluding aqueous sulfuric acid molarities greater than 1, it was possible to model the data to within experimental error by assuming only the equilibrium extraction of Cu²⁺ ion by the aggregate (HDDNS)₄(H₂O)₂₂ and the equilibrium dissociation of (HDDNS)₄(H₂O)₂₂ to the monomer. The dependence of Cu(II) distribution on aqueous sulfuric acid molarity was shown to be quantitatively consistent with a cation-exchange process. In comparison with the graphical approach, the computer analysis allows comprehensive model testing over large, nonlinear data sets and eliminates the need to make limiting assumptions. Overall, the results provide useful insight toward the development of selective synergistic extraction systems in which HDDNS provides a nonselective cation-exchange vehicle in combination with a selective second extractant.